Olefin polymerization catalysts

ABSTRACT

A catalyst composition and method for olefin polymerization are provided. In one aspect, the catalyst composition is represented by the formula α a β b γ g MX n  wherein M is a metal; X is a halogenated aryloxy group; β and γ are groups that each comprise at least one Group 15 atom; α is a linking moiety that forms a chemical bond to each of β and γ; and a, b, g, and n are each integers from 1 to 4.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of divisional applicationof Ser. No. 11/633,197, filed Dec. 4, 2006, now allowed, which is adivisional application of Ser. No. 11/193,663, filed Jul. 29, 2005,issued as U.S. Pat. No. 7,163,991, which is a divisional application ofSer. No. 10/780,438, filed Feb. 17, 2004, issued as U.S. Pat. No.6,967,184, herein incorporated by reference in their entireties.

This application is also related to Ser. No. 11/196,622, filed Aug. 3,2005, issued as U.S. Pat. No. 7,196,032.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention generally relate to olefinpolymerization catalysts. More particularly, embodiments of the presentinvention generally relate a catalyst system containing a metal atombound to at least two Group 15 atoms and their use in gas or slurryphase to produce polyolefins.

2. Description of the Related Art

Advances in polymerization and catalysis have produced new polymershaving improved physical and mechanical properties useful in a widevariety of products and applications. With the development of newcatalysts, the choice of polymerization, such as solution, slurry, highpressure or gas phase, for producing a particular polymer has beengreatly expanded. Advances in polymerization technology have alsoprovided more efficient, highly productive and economically enhancedprocesses.

Metallocene catalysts have been used to produce resins having desirableproduct properties. While these resins have excellent toughnessproperties, particularly dart impact properties, these resins can bedifficult to process. One approach to improve the processing of suchmetallocene catalyzed polyethylenes has been to blend them with anotherpolymer. While the polymer blend tends to be more processable, the blendis expensive and adds a cumbersome step to the manufacturing process.

Another approach has been to produce two polymers together at the sametime in the same reactor using two different catalysts. For example, WO99/03899 discloses using a typical metallocene catalyst and aconventional Ziegler-Natta catalyst in the same reactor to produce abimodal MWD HDPE. Other catalysts, such as anionic, multidentateheteroatom ligands, have also been used in mixed catalyst system. Forexample, U.S. Pat. No. 5,576,460 describes a preparation of arylamineligands. U.S. Pat. No. 5,889,128 discloses a process for the livingpolymerization of olefins using initiators having a metal atom and aligand having two group 15 atoms and a group 16 atom or three group 15atoms. EP 893 454 A1 describes titanium transition metal amidecompounds. U.S. Pat. No. 5,318,935 discusses amido transition metalcompounds and catalyst systems for producing isotactic polypropylene.U.S. Pat. No. 5,506,184 discloses polymerization catalysts containingbidentate and tridentate ligands.

Polymers produced by two different catalysts types, however, exhibitunpredictable characteristics. The polymers produced from two differentcatalysts can exhibit different physical and mechanical propertiescompared to the individual polymers produced separately from eachcatalyst and blends thereof. This unpredictability may occur due tocompetition or other influence between the catalyst or catalyst systemsused. This unpredictability may also occur due to differences insolubility of the individual catalyst components, reaction kinetics ofthe individual catalyst components, and the rate of decay of theindividual catalyst components, just to name a few. There is a need,therefore, for a combination of compatible catalysts capable ofproducing polyolefin polymers having desirable combinations ofprocessing, mechanical, and optical properties.

SUMMARY OF THE INVENTION

A compatible catalyst composition and method for olefin polymerizationis provided. In one aspect, the catalyst composition is represented bythe formula α_(a)β_(b)γ_(g)MX_(n) wherein M is a metal; X is ahalogenated aryloxy group; β and γ are groups that each comprise atleast one Group 15 atom; α is a linking moiety that forms a chemicalbond to each of β and γ; and a, b, g, and n are each integers from 1 to4.

In one aspect, the method for olefin polymerization comprises combiningone or more olefins with a catalyst system represented by the formula:

α_(a)β_(b)γ_(g)MX_(n)

or

wherein M is a metal;

X is a halogenated aryloxy group;

β and γ are groups that each comprise at least one Group 15 atom;

α is a linking moiety that forms a chemical bond to each of β and γ;

a, b, g, and n are each integers from 1 to 4;

y is 0 or 1;

L is a Group 15 element;

L′ is a Group 15 element;

E is a Group 15 element;

Z is a Group 15 element;

R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a heteroatomcontaining group having up to twenty carbon atoms, silicon, germanium,tin, lead, or phosphorous;

R³ is a hydrocarbon group, hydrogen, halogen, or heteroatom containinggroup;

R⁴ and R⁵ are independently an alkyl group, aryl group, substituted arylgroup, cyclic alkyl group, substituted cyclic alkyl group, cyclicarylalkyl group, substituted cyclic arylalkyl group or multiple ringsystem;

R⁶ and R⁷ are independently an alkyl group, hydrogen, halogen,heteroatom, or hydrocarbyl group; and

R* is a Group 14 atom containing group, hydrogen, halogen, or heteroatomcontaining group.

Furthermore, a method for synthesizing a pentafluorophenoxy containingcatalyst composition is provided. In one aspect, the method comprisesadding a catalyst composition represented by the formula:

α_(a)β_(b)γ_(g)MX_(n)

wherein M is a metal;

X is a halogenated aryloxy group;

β and γ are groups that each comprise at least one Group 15 atom;

α is a linking moiety that forms a chemical bond to each of β and γ; and

a, b, g, and n are each integers from 1 to 4; and

adding a sufficient amount of a trimethylsilyl derivative comprising atleast one pentafluorophenoxy group to form a metal complex comprisingthe at least one pentafluorophenoxy group.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 shows a perspective drawing of the solid-state structure for a[(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂ molecule. Non-hydrogen atomsare represented by 30% probability thermal vibration ellipsoids andhydrogen atoms are represented by arbitrarily-small spheres which are inno way representative of their true thermal motion.

FIG. 2 shows a perspective drawing of the solid-state structure for a[(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂(NMe₂H) molecule. Non-hydrogenatoms are represented by 30% probability thermal vibration ellipsoidsand hydrogen atoms are represented by arbitrarily-small spheres whichare in no way representative of their true thermal motion.

DETAILED DESCRIPTION

In one aspect, a non-metallocene catalyst for olefin polymerizationhaving improved activity, solubility and reaction kinetics is provided.In another aspect, a mixed catalyst system for olefin polymerizationthat includes the non-metallocene catalyst is also provided. The mixedcatalyst system may further include at least one metallocene catalyst.Each catalyst component of the mixed catalyst system, i.e. thenon-metallocene catalyst component and the metallocene catalystcomponent, has essentially the same rate of decay, improving catalystkinetics of the mixed catalyst system and overall product yield. Theterm “catalyst” is used interchangeably with the term “catalystcomponent”, and includes any compound or component, or combination ofcompounds or components, that is capable of increasing the rate of achemical reaction, such as the polymerization or oligomerization of oneor more olefins. The term “catalyst system” may include any number ofcatalysts in any combination as described herein, as well as anyactivator in any combination as described herein. As used herein, inreference to Periodic Table “Groups” of Elements, the “new” numberingscheme for the Periodic Table Groups are used as in the CRC HANDBOOK OFCHEMISTRY AND PHYSICS (David R. Lide ed., CRC Press 81^(st) ed. 2000).

Non-Metallocene Catalyst

The non-metallocene catalyst is preferably a Group 15-containingcatalyst. “Group 15-containing catalysts”, as referred to herein,include Group 3 to Group 12 metal complexes, wherein the metal is 2 to 4coordinate and the coordinating moiety or moieties include at least twoGroup 15 atoms, and up to four Group 15 atoms. In one embodiment, theGroup 15-containing catalyst is a complex of a Group 4 metal and fromone to four ligands such that the Group 4 metal is at least 2 coordinateand the coordinating moiety or moieties include at least two nitrogens.

In one embodiment, the Group 15-containing catalyst may include Group 4imino-phenol complexes, Group 4 bis(amide) complexes, and Group 4pyridyl-amide complexes that are active towards olefin polymerization toany extent. In another embodiment, the Group 15-containing catalyst maybe described by the following formula (I):

α_(a)β_(b)γ_(g)MX_(n)  (I)

Each X in formula (I) is independently selected from halogen ions,hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 toC20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxys, C7 to C18alkylaryloxys, halogenated C1 to C12 alkyls, halogenated C2 to C12alkenyls, halogenated C6 to C12 aryls, halogenated C7 to C20 alkylaryls,halogenated C1 to C12 alkoxys, halogenated C6 to C16 aryloxys,halogenated C7 to C18 alkylaryloxys, C1 to C12 heteroatom-containinghydrocarbons, and substituted derivatives thereof. Each X may also beselected from halogen substituted alkoxides, phenoxides, carboxylates,sulfonates, teflates, sulfides, and derivates thereof. Exemplarycarboxylates includes, but are not limited to, trifluoroacetate andpentafluorobenzoate. Exemplary sulfonates include, but are not limitedto, trifluoromethanesulfonate (“triflate”) and benzene sulfonate.Further, each X may also be selected from fluorinated alkyl amides,fluorinated alkenyl amides, fluorinated alkylaryl amides, fluorinatedalkoxy amides, fluorinated aryloxy amides, fluorinated alkylaryloxysamides, fluorinated amides, and derivates thereof. Preferably, at leastone X is a halogentated aryloxy group or a derivative thereof. Morepreferably, at least one X is a pentafluorophenoxy group.

M is selected from Group 3 to Group 12 atoms in one embodiment; andselected from Group 3 to Group 10 atoms in a more particular embodiment;and selected from Group 3 to Group 6 atoms in yet a more particularembodiment; and selected from Ni, Cr, Ti, Zr and Hf in yet a moreparticular embodiment; and selected from Zr and Hf in yet a moreparticular embodiment.

Each β and γ are groups that each comprise at least one Group 14 toGroup 16 atom; and β (when present) and γ are groups bonded to M throughbetween 2 and 6 Group 14 to Group 16 atoms, at least two atoms beingGroup 15-containing atoms.

More particularly, β and γ are groups selected from Group 14 and Group15-containing: alkyls, aryls, alkylaryls, and heterocyclic hydrocarbons,and chemically bonded combinations thereof in one embodiment; andselected from Group 14 and Group 15-containing: C₁ to C₁₀ alkyls, C₆ toC₁₂ aryls, C₆ to C₁₈ alkylaryls, and C₄ to C₁₂ heterocyclichydrocarbons, and chemically bonded combinations thereof in a moreparticular embodiment; and selected from C₁ to C₁₀ alkylamines, C₁ toC₁₀ alkoxys, C₆ to C₂₀ alkylarylamines, C₆ to C₁₈ alkylaryloxys, and C₄to C₁₂ nitrogen containing heterocyclic hydrocarbons, and C₄ to C₁₂alkyl substituted nitrogen containing heterocyclic hydrocarbons andchemically bonded combinations thereof in yet a more particularembodiment; and selected from anilinyls, pyridyls, quinolyls, pyrrolyls,pyrimidyls, purinyls, imidazyls, indolyls, C₁ to C₆ alkyl substitutedgroups selected from anilinyls, pyridyls, quinolyls, pyrrolyls,pyrimidyls, purinyls, imidazyls, indolyls; C₁ to C₆ alkylaminesubstituted groups selected from anilinyls, pyridyls, quinolyls,pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, amine substitutedanilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls,imidazyls, and indolyls; hydroxy substituted groups selected fromanilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls,imidazyls, and indolyls; methyl-substituted phenylamines, and chemicallybonded combinations thereof in yet a more particular embodiment;

Each α is a linking (or “bridging”) moiety that, when present, forms achemical bond to each of β and γ, or two γ's, thus forming a “γαγ” or“γαβ” ligand bound to M; a may also comprise a Group 14 to Group 16 atomwhich may be bonded to M through the Group 14 to Group 16 atom in oneembodiment; and more particularly, a is a divalent bridging groupselected from alkylenes, arylenes, alkenylenes, heterocyclic arylenes,alkylarylenes, heteroatom containing alkylenes, heteroatom containingalkenylenes and heterocyclic hydrocarbonylenes in one embodiment; andselected from C₁ to C₁₀ alkylenes, C₂ to C₁₀ alkenylenes, C₆ to C₁₂arylenes, C₁ to C₁₀ divalent ethers, C₆ to C₁₂ O- or N-containingarylenes, C₂ to C₁₀ alkyleneamines, C₆ to C₁₂ aryleneamines, andsubstituted derivatives thereof in yet a more particular embodiment;

a is an integer from 0 to 2; a is either 0 or 1 in a more particularembodiment; and a is 1 in yet a more particular embodiment; b is aninteger from 0 to 2; g is an integer from 1 to 2; wherein in oneembodiment, a is 1, b is 0 and g is 2; and

n is an integer from 0 to 4 in one embodiment; and an integer from 1 to3 in a more particular embodiment; and an integer from 2 to 3 in yet amore particular embodiment.

As used herein, “chemically bonded combinations thereof” means thatadjacent groups, (β and γ groups) may form a chemical bond between them.In one embodiment, the β and γ groups are chemically bonded through oneor more α groups there between.

As used herein, the terms “alkyleneamines” and “aryleneamines” describealkylamines and arylamines (respectively) that are deficient by twohydrogens, thus forming chemical bonds with two adjacent γ groups, oradjacent β and γ groups. Thus, an example of an alkyleneamine is—CH₂CH₂N(CH₃)CH₂CH₂—, and an example of a heterocyclic hydrocarbylene orarylene amine is —C₅H₃N-(divalent pyridine). An “alkylene-arylamine” isa group such as, for example, —CH₂CH₂(C₅H₃N)CH₂CH₂—.

In another embodiment, the Group 15-containing catalyst may berepresented by the structures (II) and (III):

Each X in formulas (II) and (III) is independently selected from halogenions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls,C7 to C20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxys, C7 to C18alkylaryloxys, halogenated C1 to C12 alkyls, halogenated C2 to C12alkenyls, halogenated C6 to C12 aryls, halogenated C7 to C20 alkylaryls,halogenated C1 to C12 alkoxys, halogenated C6 to C16 aryloxys,halogenated C7 to C18 alkylaryloxys, C1 to C12 heteroatom-containinghydrocarbons, and substituted derivatives thereof. Each X may also beselected from halogen substituted alkoxides, phenoxides, carboxylates,sulfonates, teflates, sulfides, and derivates thereof. Exemplarycarboxylates includes, but are not limited to, trifluoroacetate andpentafluorobenzoate. Exemplary sulfonates include, but are not limitedto, trifluoromethanesulfonate (“triflate”) and benzene sulfonate.Further, each X may also be selected from fluorinated alkyl amides,fluorinated alkenyl amides, fluorinated alkylaryl amides, fluorinatedalkoxy amides, fluorinated aryloxy amides, fluorinated alkylaryloxysamides, fluorinated amides, and derivates thereof. Preferably, at leastone X is a halogentated aryloxy group or a derivative thereof. Morepreferably, at least one X is a pentafluorophenoxy group.

E and Z are Group 15 elements independently selected from nitrogen andphosphorus in one embodiment; and nitrogen in a more particularembodiment;

L is selected from Group 15 atoms, Group 16 atoms, Group 15-containinghydrocarbylenes and a Group 16 containing hydrocarbylenes in oneembodiment; wherein R³ is absent when L is a Group 16 atom; in yet amore particular embodiment, when R³ is absent, L is selected fromheterocyclic hydrocarbylenes; and in yet a more particular embodiment, Lis selected from nitrogen, phosphorous, anilinyls, pyridyls, quinolyls,pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; C₁ to C₆ alkylsubstituted groups selected from anilinyls, pyridyls, quinolyls,pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; C₁ to C₆alkylamine substituted groups selected from anilinyls, pyridyls,quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; aminesubstituted anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls,purinyls, imidazyls, and indolyls; hydroxy substituted groups selectedfrom anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls,imidazyls, and indolyls; methyl-substituted phenylamines, substitutedderivatives thereof, and chemically bonded combinations thereof;

L′ is selected from Group 15 atoms, Group 16 atoms, and Group 14 atomsin one embodiment; and selected from Group 15 and Group 16 atoms in amore particular embodiment; and is selected from groups as defined by Labove in yet a more particular embodiment, wherein “EZL” and “EZL′” maybe referred to as a “ligand”, the EZL and EZL′ ligands comprising the R*and R¹-R⁷ groups;

L and L′ may or may not form a bond with M;

y is an integer ranging from 0 to 2 (when y is 0, group L′, *R and R³are absent);

M is selected from Group 3 to Group 5 atoms, Group 4 atoms in a moreparticular embodiment, and selected from Zr and Hf in yet a moreparticular embodiment;

n is an integer ranging from 1 to 4 in one embodiment; n is an integerranging from 2 to 3 in a more particular embodiment;

R¹ and R² are independently: divalent bridging groups selected fromalkylenes, arylenes, heteroatom containing alkylenes, heteroatomcontaining arylenes, substituted alkylenes, substituted arylenes andsubstituted heteroatom containing alkylenes, wherein the heteroatom isselected from silicon, oxygen, nitrogen, germanium, phosphorous, boronand sulfur in one embodiment; selected from C₁ to C₂₀ alkylenes, C₆ toC₁₂ arylenes, heteroatom-containing C₁ to C₂₀ alkylenes andheteroatom-containing C₆ to C₁₂ arylenes in a more particularembodiment; and in yet a more particular embodiment selected from —CH₂—,—C(CH₃)₂—, —C(C₆H₅)₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —Si(CH₃)₂—, —Si(C₆H₅)₂—,—C₆H₁₀—, —C₆H₄—, and substituted derivatives thereof, the substitutionsincluding C₁ to C₄ alkyls, phenyl, and halogen radicals;

R³ is absent in one embodiment; a group selected from hydrocarbylgroups, hydrogen radical, halogen radicals, and heteroatom-containinggroups in a more particular embodiment; and selected from linear alkyls,cyclic alkyls, and branched alkyls having 1 to 20 carbon atoms in yet amore particular embodiment;

*R is absent in one embodiment; a group selected from hydrogen radical,Group 14 atom containing groups, halogen radicals, and aheteroatom-containing groups in yet a more particular embodiment;

R⁴ and R⁵ are independently: groups selected from alkyls, aryls,substituted aryls, cyclic alkyls, substituted cyclic alkyls, cyclicarylalkyls, substituted cyclic arylalkyls and multiple ring systems inone embodiment, each group having up to 20 carbon atoms, and between 3and 10 carbon atoms in a more particular embodiment; selected from C₁ toC₂₀ alkyls, C₁ to C₂₀ aryls, C₁ to C₂₀ arylalkyls, andheteroatom-containing groups (for example PR₃, where R is an alkylgroup) in yet a more particular embodiment; and

R¹ and R⁷ are independently: absent in one embodiment; groups selectedfrom hydrogen radicals, halogen radicals, heteroatom-containing groupsand hydrocarbyls in a more particular embodiment; selected from linear,cyclic and branched alkyls having from 1 to 20 carbon atoms in yet amore particular embodiment;

R¹ and R² may be associated with one another, and/or R⁴ and R⁵ may beassociated with one another as through a chemical bond.

In yet another embodiment, the Group 15-containing catalyst may berepresented by the structures (IV), (V) and (VI) (where “N” isnitrogen):

The structure (IV) represents pyridyl-amide structures, the structure(V) represents imino-phenol structures, and the structure (VI)represents bis(amide) structures. Each X in formulas (IV-VI) isindependently selected from halogen ions, hydrides, C1 to C12 alkyls, C2to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12alkoxys, C6 to C16 aryloxys, C7 to C18 alkylaryloxys, halogenated C1 toC12 alkyls, halogenated C2 to C12 alkenyls, halogenated C6 to C12 aryls,halogenated C7 to C20 alkylaryls, halogenated C1 to C12 alkoxys,halogenated C6 to C16 aryloxys, halogenated C7 to C18 alkylaryloxys, C1to C12 heteroatom-containing hydrocarbons, and substituted derivativesthereof. Each X may also be selected from halogen substituted alkoxides,phenoxides, carboxylates, sulfonates, teflates, sulfides, and derivatesthereof. Exemplary carboxylates includes, but are not limited to,trifluoroacetate and pentafluorobenzoate. Exemplary sulfonates include,but are not limited to, trifluoromethanesulfonate (“triflate”) andbenzene sulfonate. Further, each X may also be selected from fluorinatedalkyl amides, fluorinated alkenyl amides, fluorinated alkylaryl amides,fluorinated alkoxy amides, fluorinated aryloxy amides, fluorinatedalkylaryloxys amides, fluorinated amides, and derivates thereof.Preferably, at least one X is a halogentated aryloxy group or aderivative thereof. More preferably, at least one X is apentafluorophenoxy group.

w is an integer from 1 to 3, and 1 or 2 in a more particular embodiment,and 1 in yet a more particular embodiment; M is a Group 3 to Group 13element, a Group 3 to Group 6 element in a more particular embodiment,and a Group 4 element in yet a more particular embodiment; and n is aninteger ranging from 0 to 4, and from 1 to 3 in a more particularembodiment, and from 2 to 3 in yet a more particular embodiment, and 2in yet a more particular embodiment.

In structures (IV), (V), and (VI), R¹′ is selected from hydrocarbylenesand heteroatom-containing hydrocarbylenes in one embodiment, andselected from —SiR₂—, alkylenes, arylenes, alkenylenes and substitutedalkylenes, substituted alkenylenes and substituted arylenes in anotherembodiment; and selected from —SiR₂—, C₁ to C₆ alkylenes, C₆ to C₁₂arylenes, C₁ to C₆ substituted alkylenes and C₆ to C₁₂ substitutedarylenes in another embodiment.

R is selected from C₁ to C₆ alkyls and C₆ to C₁₂ aryls; and R²′, R³′,R⁴′, R⁵′, R⁶′ and R* are independently selected from hydride, C₁ to C₁₀alkyls, C₆ to C₁₂ aryls, C₆ to C₁₈ alkylaryls, C₄ to C₁₂ heterocyclichydrocarbyls, substituted C₁ to C₁₀ alkyls, substituted C₆ to C₁₂ aryls,substituted C₆ to C₁₈ alkylaryls, and substituted C₄ to C₁₂ heterocyclichydrocarbyls and chemically bonded combinations thereof in oneembodiment.

R* is absent in a particular embodiment; and in another embodiment, R*-Nrepresents a nitrogen containing group or ring such as a pyridyl groupor a substituted pyridyl group that is bridged by the R¹′ groups. In yetanother embodiment, R*-N is absent, and the R¹′ groups form a chemicalbond to one another.

In one embodiment of structures (IV), (V), and (VI), R¹′ is selectedfrom methylene, ethylene, 1-propylene, 2-propylene, ═Si(CH₃)₂,═Si(phenyl)₂, —CH═, —C(CH₃)═, —C(phenyl)₂-, —C(phenyl)=(wherein “═”represents two chemical bonds), and the like.

In a particular embodiment of structure (V), R²′ and R⁴′ are selectedfrom 2-methylphenyl, 2-n-propylphenyl, 2-iso-propylphenyl,2-iso-butylphenyl, 2-tert-butylphenyl, 2-fluorophenyl, 2-chlorophenyl,2-bromophenyl, 2-methyl-4-chlorophenyl, 2-n-propyl-4-chlorophenyl,2-iso-propyl-4-chlorophenyl, 2-iso-butyl-4-chlorophenyl,2-tert-butyl-4-chlorophenyl, 2-methyl-4-fluorophenyl,2-n-propyl-4-fluorophenyl, 2-iso-propyl-4-fluorophenyl,2-iso-butyl-4-fluorophenyl, 2-tert-butyl-4-fluorophenyl,2-methyl-4-bromophenyl, 2-n-propyl-4-bromophenyl,2-iso-propyl-4-bromophenyl, 2-iso-butyl-4-bromophenyl,2-tert-butyl-4-bromophenyl, and the like.

In yet another particular embodiment of structures (IV) and (VI), R²′and R³′ are selected from 2-methylphenyl, 2-n-propylphenyl,2-iso-propylphenyl, 2-iso-butylphenyl, 2-tert-butylphenyl,2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 4-methylphenyl,4-n-propylphenyl, 4-iso-propylphenyl, 4-iso-butylphenyl,4-tert-butylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl,6-methylphenyl, 6-n-propylphenyl, 6-iso-propylphenyl, 6-iso-butylphenyl,6-tert-butylphenyl, 6-fluorophenyl, 6-chlorophenyl, 6-bromophenyl,2,6-dimethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-iso-propylphenyl,2,6-di-isobutylphenyl, 2,6-di-tert-butylphenyl, 2,6-difluorophenyl,2,6-dichlorophenyl, 2,6-dibromophenyl, 2,4,6-trimethylphenyl,2,4,6-tri-n-propylphenyl, 2,4,6-tri-iso-propylphenyl,2,4,6-tri-iso-butylphenyl, 2,4,6-tri-tert-butylphenyl,2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl,2,3,4,5,6-pentafluorophenyl, 2,3,4,5,6-pentachlorophenyl,2,3,4,5,6-pentabromophenyl, and the like.

As used here, “chemically bonded combinations” means that adjacentgroups may form a chemical bond between them, thus forming a ringsystem, either saturated, partially unsaturated, or aromatic.

In still yet another embodiment, the Group 15-containing catalyst may berepresented by the structures (VIIa)-(VIIf) (where “N” is nitrogen):

In structures (VIIa) through (VIIf) M is selected from Group 4 atoms inone embodiment; and M is selected from Zr and Hf in a more particularembodiment; n is an integer ranging from 0 to 4, and from 2 to 3 in amore particular embodiment; and R¹ through R¹¹ in structures (VIIa)through (VIIf) are selected from hydride, fluorine radical, chlorineradical, bromine radical, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl and phenyl.

Each X in formulas (VIIa)-(VIIf) is independently selected from halogenions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls,C7 to C20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxys, C7 to C18alkylaryloxys, halogenated C1 to C12 alkyls, halogenated C2 to C12alkenyls, halogenated C6 to C12 aryls, halogenated C7 to C20 alkylaryls,halogenated C1 to C12 alkoxys, halogenated C6 to C16 aryloxys,halogenated C7 to C18 alkylaryloxys, C1 to C12 heteroatom-containinghydrocarbons, and substituted derivatives thereof. Each X may also beselected from halogen substituted alkoxides, phenoxides, carboxylates,sulfonates, teflates, sulfides, and derivates thereof. Exemplarycarboxylates includes, but are not limited to, trifluoroacetate andpentafluorobenzoate. Exemplary sulfonates include, but are not limitedto, trifluoromethanesulfonate (“triflate”) and benzene sulfonate.Further, each X may also be selected from fluorinated alkyl amides,fluorinated alkenyl amides, fluorinated alkylaryl amides, fluorinatedalkoxy amides, fluorinated aryloxy amides, fluorinated alkylaryloxysamides, fluorinated amides, and derivates thereof. Preferably, at leastone X is a halogentated aryloxy group or a derivative thereof. Morepreferably, at least one X is a pentafluorophenoxy group.

Mixed Catalyst

The mixed catalyst system may be described as a bimetallic catalystcomposition or a multi-catalyst composition. As used herein, the terms“bimetallic catalyst composition” and “bimetallic catalyst” include anycomposition, mixture, or system that includes two or more differentcatalyst components, each having a different metal group. The terms“multi-catalyst composition” and “multi-catalyst” include anycomposition, mixture, or system that includes two or more differentcatalyst components regardless of the metals. Therefore, the terms“bimetallic catalyst composition,” “bimetallic catalyst,”“multi-catalyst composition,” and “multi-catalyst” will be collectivelyreferred to as a “mixed catalyst system,” unless specifically notedotherwise.

Metallocene Catalyst Component

As mentioned above, the mixed catalyst system includes the Group15-containing catalyst described above and one or more metallocenecatalyst components. The metallocene catalyst component may include“half sandwich” and “full sandwich” compounds having one or more Cpligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl)bound to at least one Group 3 to Group 12 metal atom, and one or moreleaving group(s) bound to the at least one metal atom.

The Cp ligands are one or more rings or ring system(s), at least aportion of which includes π-bonded systems, such as cycloalkadienylligands and heterocyclic analogues. The ring(s) or ring system(s)typically comprise atoms selected from the group consisting of Groups 13to 16 atoms, and more particularly, the atoms that make up the Cpligands are selected from the group consisting of carbon, nitrogen,oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum andcombinations thereof, wherein carbon makes up at least 50% of the ringmembers. Even more particularly, the Cp ligand(s) are selected from thegroup consisting of substituted and unsubstituted cyclopentadienylligands and ligands isolobal to cyclopentadienyl, non-limiting examplesof which include cyclopentadienyl, indenyl, fluorenyl and otherstructures. Further non-limiting examples of such ligands includecyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl,fluorenyl, octahydrofluorenyl, cyclooctatetraenyl,cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl,9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl,indeno[1, 2-9]anthrene, thiophenoindenyl, thiophenofluorenyl,hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or“H₄Ind”), substituted versions thereof (as described in more detailbelow), and heterocyclic versions thereof.

The metal atom “M” of the metallocene catalyst compound, may be selectedfrom the group consisting of Groups 3 through 12 atoms and lanthanideGroup atoms in one embodiment; and selected from the group consisting ofGroups 3 through 10 atoms in a more particular embodiment, and selectedfrom the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru,Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selectedfrom the group consisting of Groups 4, 5 and 6 atoms in yet a moreparticular embodiment, and a Ti, Zr, Hf atoms in yet a more particularembodiment, and Zr in yet a more particular embodiment. The oxidationstate of the metal atom “M” may range from 0 to +7 in one embodiment;and in a more particular embodiment, is +1, +2, +3, +4 or +5; and in yeta more particular embodiment is +2, +3 or +4.

The groups bound to the metal atom “M” are such that the compoundsdescribed below in the formulas and structures are neutral, unlessotherwise indicated. The Cp ligand(s) form at least one chemical bondwith the metal atom M to form the “metallocene catalyst compound.” TheCp ligands are distinct from the leaving groups bound to the catalystcompound in that they are not highly susceptible tosubstitution/abstraction reactions.

In one aspect, the one or more metallocene catalyst components arerepresented by the formula (VIII):

Cp^(A)Cp^(B)MX_(n)  (VIII)

wherein M is as described above; each X is chemically bonded to M; eachCp group is chemically bonded to M; and n is 0 or an integer from 1 to4, and either 1 or 2 in a particular embodiment.

The ligands represented by Cp^(A) and Cp^(B) in formula (VIII) may bethe same or different cyclopentadienyl ligands or ligands isolobal tocyclopentadienyl, either or both of which may contain heteroatoms andeither or both of which may be substituted by a group R. In oneembodiment, Cp^(A) and Cp^(B) are independently selected from the groupconsisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (VIII) may beunsubstituted or substituted with any one or combination of substituentgroups R. Non-limiting examples of substituent groups R as used instructure (II) include hydrogen radicals, alkyls, alkenyls, alkynyls,cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols,dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls,carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos,aroylaminos, and combinations thereof.

More particular non-limiting examples of alkyl substituents R associatedwith formula (II) includes methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, andtert-butylphenyl groups and the like, including all their isomers, forexample tertiary-butyl, isopropyl, and the like. Other possible radicalsinclude substituted alkyls and aryls such as, for example, fluoromethyl,fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl andhydrocarbyl substituted organometalloid radicals includingtrimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted Group 15 radicalsincluding dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, Group 16 radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents Rinclude olefins such as but not limited to olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example 3-butenyl,2-propenyl, 5-hexenyl and the like. In one embodiment, at least two Rgroups, two adjacent R groups in one embodiment, are joined to form aring structure having from 3 to 30 atoms selected from the groupconsisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium,aluminum, boron and combinations thereof. Also, a substituent group Rgroup such as 1-butanyl may form a bonding association to the element M.

Each X in formula (VIII) is independently selected from the following:halogen ions, hydrides, C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇to C₁₈ alkylaryloxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, andC₁ to C₁₂ heteroatom-containing hydrocarbons and substituted derivativesthereof in a more particular embodiment; hydride, halogen ions, C₁ to C₆alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ alkoxys, C₆ toC₁₄ aryloxys, C₇ to C₁₆ alkylaryloxys, C₁ to C₆ alkylcarboxylates, C₁ toC₆ fluorinated alkylcarboxylates, C₆ to C₁₂ arylcarboxylates, C₇ to C₁₈alkylarylcarboxylates, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls,and C₇ to C₁₈ fluoroalkylaryls in yet a more particular embodiment;hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl,fluoromethyls and fluorophenyls in yet a more particular embodiment; C₁to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀alkylaryls, substituted C₁ to C₁₂ alkyls, substituted C₆ to C₁₂ aryls,substituted C₇ to C₂₀ alkylaryls and C₁ to C₁₂ heteroatom-containingalkyls, C₁ to C₁₂ heteroatom-containing aryls and C₁ to C₁₂heteroatom-containing alkylaryls in yet a more particular embodiment;chloride, fluoride, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈alkylaryls, halogenated C₁ to C₆ alkyls, halogenated C₂ to C₆ alkenyls,and halogenated C₇ to C₁₈ alkylaryls in yet a more particularembodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl,dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- andtrifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- andpentafluorophenyls) in yet a more particular embodiment.

Other non-limiting examples of X groups in formula (VIII) includeamines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicalshaving from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals(e.g., —C₆F₅ (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g.,CF₃C(O)O⁻), hydrides and halogen ions and combinations thereof. Otherexamples of X ligands include alkyl groups such as cyclobutyl,cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike. In one embodiment, two or more X's form a part of a fused ring orring system.

In another aspect, the metallocene catalyst component includes those offormula (VIII) where Cp^(A) and Cp^(B) are bridged to each other by atleast one bridging group, (A), such that the structure is represented byformula (IX):

Cp^(A)(A)Cp^(B)MX_(n)  (IX)

These bridged compounds represented by formula (IX) are known as“bridged metallocenes”. CP^(A), CP^(B), M, X and n are as defined abovefor formula (VIII); and wherein each Cp ligand is chemically bonded toM, and (A) is chemically bonded to each Cp. Non-limiting examples ofbridging group (A) include divalent hydrocarbon groups containing atleast one Group 13 to 16 atom, such as but not limited to at least oneof a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium andtin atom and combinations thereof; wherein the heteroatom may also be C₁to C₁₂ alkyl or aryl substituted to satisfy neutral valency.

The bridging group (A) may also contain substituent groups R as definedabove for formula (VIII) including halogen radicals and iron. Moreparticular non-limiting examples of bridging group (A) are representedby C₁ to C₆ alkylenes, substituted C₁ to C₆ alkylenes, oxygen, sulfur,R′₂C═, R′₂Si═, —Si(R′)₂Si(R′₂), R′₂Ge═, R′P═ (wherein “═” represents twochemical bonds), where R′ is independently selected from the groupconsisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted Group 15 atoms, substituted Group 16 atoms, and halogenradical; and wherein two or more R′ may be joined to form a ring or ringsystem. In one embodiment, the bridged metallocene catalyst component offormula (IX) has two or more bridging groups (A).

Other non-limiting examples of bridging group (A) include methylene,ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene,1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene,dimethylsilyl, diethylsilyl, methyl-ethylsilyl,trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl,di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl,dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl,t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and thecorresponding moieties wherein the Si atom is replaced by a Ge or a Catom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

In another embodiment, bridging group (A) may also be cyclic,comprising, for example 4 to 10, 5 to 7 ring members in a moreparticular embodiment. The ring members may be selected from theelements mentioned above, from one or more of B, C, Si, Ge, N and O in aparticular embodiment. Non-limiting examples of ring structures whichmay be present as or part of the bridging moiety are cyclobutylidene,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene andthe corresponding rings where one or two carbon atoms are replaced by atleast one of Si, Ge, N and O, in particular, Si and Ge. The bondingarrangement between the ring and the Cp groups may be either cis-,trans-, or a combination.

The cyclic bridging groups (A) may be saturated or unsaturated and/orcarry one or more substituents and/or be fused to one or more other ringstructures. If present, the one or more substituents are selected fromthe group consisting of hydrocarbyl (e.g., alkyl such as methyl) andhalogen (e.g., F, Cl) in one embodiment. The one or more Cp groups whichthe above cyclic bridging moieties may optionally be fused to may besaturated or unsaturated and are selected from the group consisting ofthose having 4 to 10, more particularly 5, 6 or 7 ring members (selectedfrom the group consisting of C, N, O and S in a particular embodiment)such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover,these ring structures may themselves be fused such as, for example, inthe case of a naphthyl group. Moreover, these (optionally fused) ringstructures may carry one or more substituents. Illustrative,non-limiting examples of these substituents are hydrocarbyl(particularly alkyl) groups and halogen atoms.

The ligands Cp^(A) and Cp^(B) of formula (VIII) and (IX) are differentfrom each other in one embodiment, and the same in another embodiment.

In yet another aspect, the metallocene catalyst components includemono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalystcomponents) such as described in WO 93/08221 for example. In thisembodiment, the at least one metallocene catalyst component is a bridged“half-sandwich” metallocene represented by the formula (X):

Cp^(A)(A)QMX_(n)  (X)

wherein Cp^(A) is defined above with reference to formula (VIII) and isbound to M; (A) is a bridging group bonded to Q and Cp^(A); and whereinan atom from the Q group is bonded to M; and n is 0 or an integer from 1to 3; 1 or 2 in a particular embodiment. In formula (X), Cp^(A), (A) andQ may form a fused ring system. The X groups and n of formula (X) are asdefined above in formula (VIII) and (IX). In one embodiment, Cp^(A) isselected from the group consisting of cyclopentadienyl, indenyl,tetrahydroindenyl, fluorenyl, substituted versions thereof, andcombinations thereof.

In formula (X), Q is a heteroatom-containing ligand in which the bondingatom (the atom that is bonded with the metal M) is selected from thegroup consisting of Group 15 atoms and Group 16 atoms in one embodiment,and selected from the group consisting of nitrogen, phosphorus, oxygenor sulfur atom in a more particular embodiment, and nitrogen and oxygenin yet a more particular embodiment. Non-limiting examples of Q groupsinclude alkylamines, arylamines, mercapto compounds, ethoxy compounds,carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene,phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzeneother compounds comprising Group 15 and Group 16 atoms capable ofbonding with M.

In yet another aspect, the at least one metallocene catalyst componentis an unbridged “half sandwich” metallocene represented by the formula(XI):

Cp^(A)MQ_(q)X_(n)  (XI)

wherein Cp^(A) is defined as for the Cp groups in (VIII) and is a ligandthat is bonded to M; each Q is independently bonded to M; Q is alsobound to Cp^(A) in one embodiment; X is a leaving group as describedabove in (VIII); n ranges from 0 to 3, and is 1 or 2 in one embodiment;q ranges from 0 to 3, and is 1 or 2 in one embodiment. In oneembodiment, Cp^(A) is selected from the group consisting ofcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substitutedversion thereof, and combinations thereof.

In formula (XII), Q is selected from the group consisting of ROO⁻, RO—,R(O)—, —NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, andsubstituted and unsubstituted aryl groups, wherein R is selected fromthe group consisting of C₁ to C₆ alkyls, C₆ to C₁₂ aryls, C₁ to C₆alkylamines, C₆ to C₁₂ alkylarylamines, C₁ to C₆ alkoxys, C₆ to C₁₂aryloxys, and the like. Non-limiting examples of Q include C₁ to C₁₂carbamates, C₁ to C₁₂ carboxylates (e.g., pivalate), C₂ to C₂₀ alkyls,and C₂ to C₂₀ heteroallyl moieties.

Described another way, the “half sandwich” metallocenes above can bedescribed as in for example, U.S. Pat. No. 6,069,213:

Cp^(A)M(Q₂GZ)X_(n) or T(Cp^(A)M(Q₂GZ)X_(n))_(m)  (XII)

wherein M, Cp^(A), X and n are as defined above;

Q₂GZ forms a polydentate ligand unit (e.g., pivalate), wherein at leastone of the Q groups form a bond with M, and is defined such that each Qis independently selected from the group consisting of —O—, —NR—, —CR₂—and —S—; G is either carbon or silicon; and Z is selected from the groupconsisting of R, —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, and hydride,providing that when Q is —NR—, then Z is selected from the groupconsisting of —OR, —NR₂, —SR, —SiR₃, —PR₂; and provided that neutralvalency for Q is satisfied by Z; and wherein each R is independentlyselected from the group consisting of C₁ to C₁₀ heteroatom containinggroups, C₁ to C₁₀ alkyls, C₆ to C₁₂ aryls, C₆ to C₁₂ alkylaryls, C₁ toC₁₀ alkoxys, and C₆ to C₁₂ aryloxys;

n is 1 or 2 in a particular embodiment; and

T is a bridging group selected from the group consisting of C₁ to C₁₀alkylenes, C₆ to C₁₂ arylenes and C₁ to C₁₀ heteroatom containinggroups, and C₆ to C₁₂ heterocyclic groups; wherein each T group bridgesadjacent “Cp^(A)M(Q₂GZ)X_(n)” groups, and is chemically bonded to theCp^(A) groups.

m is an integer from 1 to 7; m is an integer from 2 to 6 in a moreparticular embodiment.

In another aspect, the at least one metallocene catalyst component canbe described more particularly in structures (XIIIa), (XIIIb), (XIIIc),(XIIId), (XIIIe), and (XIIIf):

wherein in structures (XIIIa) to (XIIIf), M is selected from the groupconsisting of Group 3 to Group 12 atoms, and selected from the groupconsisting of Group 3 to Group 10 atoms in a more particular embodiment,and selected from the group consisting of Group 3 to Group 6 atoms inyet a more particular embodiment, and selected from the group consistingof Group 4 atoms in yet a more particular embodiment, and selected fromthe group consisting of Zr and Hf in yet a more particular embodiment;and is Zr in yet a more particular embodiment;

wherein Q in (XIIIa) to (XIIIf) is selected from the group consisting ofalkylenes, aryls, arylenes, alkoxys, aryloxys, amines, arylamines (e.g.,pyridyl) alkylamines, phosphines, alkylphosphines, substituted alkyls,substituted aryls, substituted alkoxys, substituted aryloxys,substituted amines, substituted alkylamines, substituted phosphines,substituted alkylphosphines, carbamates, heteroallyls, carboxylates(non-limiting examples of suitable carbamates and carboxylates includetrimethylacetate, trimethylacetate, methylacetate, p-toluate, benzoate,diethylcarbamate, and dimethylcarbamate), fluorinated alkyls,fluorinated aryls, and fluorinated alkylcarboxylates; wherein thesaturated groups defining Q comprise from 1 to 20 carbon atoms in oneembodiment; and wherein the aromatic groups comprise from 5 to 20 carbonatoms in one embodiment;

wherein each R* is independently: selected from the group consisting ofhydrocarbylenes and heteroatom-containing hydrocarbylenes in oneembodiment; and selected from the group consisting of alkylenes,substituted alkylenes and heteroatom-containing hydrocarbylenes inanother embodiment; and selected from the group consisting of C₁ to C₁₂alkylenes, C₁ to C₁₂ substituted alkylenes, and C₁ to C₁₂heteroatom-containing hydrocarbylenes in a more particular embodiment;and selected from the group consisting of C₁ to C₄ alkylenes in yet amore particular embodiment; and wherein both R* groups are identical inanother embodiment in structures (XIIIf);

A is as described above for (A) in structure (IX), and moreparticularly, selected from the group consisting of a chemical bond,—O—, —S—, —SO₂—, —NR—, ═SiR₂, ═GeR₂, ═SnR₂, —R₂SiSiR₂—, RP═, C₁ to C₁₂alkylenes, substituted C₁ to C₁₂ alkylenes, divalent C₄ to C₁₂ cyclichydrocarbons and substituted and unsubstituted aryl groups in oneembodiment; and selected from the group consisting of C₅ to C₈ cyclichydrocarbons, —CH₂CH₂—, ═CR₂ and ═SiR₂ in a more particular embodiment;wherein and R is selected from the group consisting of alkyls,cycloalkyls, aryls, alkoxys, fluoroalkyls and heteroatom-containinghydrocarbons in one embodiment; and R is selected from the groupconsisting of C₁ to C₆ alkyls, substituted phenyls, phenyl, and C₁ to C₆alkoxys in a more particular embodiment; and R is selected from thegroup consisting of methoxy, methyl, phenoxy, and phenyl in yet a moreparticular embodiment;

wherein A may be absent in yet another embodiment, in which case each R*is defined as for R¹-R¹³;

each X is as described above in (VIII);

n is an integer from 0 to 4, and from 1 to 3 in another embodiment, and1 or 2 in yet another embodiment; and

R¹ through R¹³ are independently: selected from the group consisting ofhydrogen radical, halogen radicals, C₁ to C₁₂ alkyls, C₂ to C₁₂alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₁to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ to C₁₂heteroatom-containing hydrocarbons and substituted derivatives thereofin one embodiment; selected from the group consisting of hydrogenradical, fluorine radical, chlorine radical, bromine radical, C₁ to C₆alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ fluoroalkyls,C₂ to C₆ fluoroalkenyls, C₇ to C₁₈ fluoroalkylaryls in a more particularembodiment; and hydrogen radical, fluorine radical, chlorine radical,methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl,hexyl, phenyl, 2,6-di-methylpheyl, and 4-tertiarybutylpheyl groups inyet a more particular embodiment; wherein adjacent R groups may form aring, either saturated, partially saturated, or completely saturated.

The structure of the metallocene catalyst component represented by(XIIIa) may take on many forms such as disclosed in, for example, U.S.Pat. No. 5,026,798, U.S. Pat. No. 5,703,187, and U.S. Pat. No.5,747,406, including a dimmer or oligomeric structure, such as disclosedin, for example, U.S. Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213.

In a particular embodiment of the metallocene represented in (XIIId), R¹and R² form a conjugated 6-membered carbon ring system that may or maynot be substituted.

Non-limiting examples of metallocene catalyst components consistent withthe description herein include: cyclopentadienylzirconium X_(n),

-   indenylzirconium X_(n),-   (1-methylindenyl)zirconium X_(n),-   (2-methylindenyl)zirconium X_(n),-   (1-propylindenyl)zirconium X_(n),-   (2-propylindenyl)zirconium X_(n),-   (1-butylindenyl)zirconium X_(n),-   (2-butylindenyl)zirconium X_(n),-   (methylcyclopentadienyl)zirconium X_(n),-   tetrahydroindenylzirconium X_(n),-   (pentamethylcyclopentadienyl)zirconium X_(n),-   cyclopentadienylzirconium X_(n),-   pentamethylcyclopentadienyltitanium X_(n),-   tetramethylcyclopentyltitanium X_(n),-   1,2,4-trimethylcyclopentadienylzirconium X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethyl-cyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethyl-cyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(2-methylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(cyclopentadienyl)(indenyl)zirconium X_(n),-   dimethylsilyl(2-methylindenyl)(fluorenyl)zirconium X_(n),-   diphenylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-propylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-t-butylcyclopentadienyl)zirconium    X_(n),-   dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-methylcyclopentadienyl)    zirconium X_(n),-   diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylmethylidene(cyclopentadienyl)(indenyl)zirconium X_(n),-   iso-propylidenebis(cyclopentadienyl)zirconium X_(n),-   iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   iso-propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconium    X_(n),-   ethylenebis(9-fluorenyl)zirconium X_(n),-   meso-ethylenebis(1-indenyl)zirconium X_(n),-   ethylenebis(1-indenyl)zirconium X_(n),-   ethylenebis(2-methyl-1-indenyl)zirconium X_(n),-   ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconium    X_(n),-   ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),-   dimethylsilylbis(cyclopentadienyl)zirconium X_(n),-   dimethylsilylbis(9-fluorenyl)zirconium X_(n),-   dimethylsilylbis(1-indenyl)zirconium X_(n),-   dimethylsilylbis(2-methylindenyl)zirconium X_(n),-   dimethylsilylbis(2-propylindenyl)zirconium X_(n),-   dimethylsilylbis(2-butylindenyl)zirconium X_(n),-   diphenylsilylbis(2-methylindenyl)zirconium X_(n),-   diphenylsilylbis(2-propylindenyl)zirconium X_(n),-   diphenylsilylbis(2-butylindenyl)zirconium X_(n),-   dimethylgermylbis(2-methylindenyl)zirconium X,-   dimethylsilylbis(tetrahydroindenyl)zirconium X_(n),-   dimethylsilylbis(tetramethylcyclopentadienyl)zirconium X_(n),-   dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),-   diphenylsilylbis(indenyl)zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium    X_(n),-   cyclotetramethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)    zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2-methylindenyl)zirconium    cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilylbis(2-methylindenyl)zirconium X_(n),-   cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylcyclopentadienyl)zirconium    X_(n),-   cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconium    X_(n),-   dimethylsilyl(tetramethylcyclopentadieneyl)(N-tert-butylamido)titanium    X_(n),-   bis(cyclopentadienyl)chromium X_(n),-   bis(cyclopentadienyl)zirconium X_(n),-   bis(n-butylcyclopentadienyl)zirconium X_(n),-   bis(n-dodecyclcyclopentadienyl)zirconium X_(n),-   bis(ethylcyclopentadienyl)zirconium X_(n),-   bis(iso-butylcyclopentadienyl)zirconium X_(n),-   bis(iso-propylcyclopentadienyl)zirconium X_(n),-   bis(methylcyclopentadienyl)zirconium X_(n),-   bis(n-oxtylcyclopentadienyl)zirconium X_(n),-   bis(n-pentylcyclopentadienyl)zirconium X_(n),-   bis(n-propylcyclopentadienyl)zirconium X_(n),-   bis(trimethylsilylcyclopentadienyl)zirconium X_(n),-   bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconium X_(n),-   bis(1-ethyl-2-methylcyclopentadienyl)zirconium X_(n),-   bis(1-ethyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(pentamethylcyclopentadienyl)zirconium X_(n),-   bis(pentamethylcyclopentadienyl)zirconium X_(n),-   bis(1-propyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-n-butyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-isobutyl-3-methylcyclopentadienyl)zirconium X_(n),-   bis(1-propyl-3-butylcyclopentadienyl)zirconium X_(n),-   bis(1,3-n-butylcyclopentadienyl)zirconium X_(n),-   bis(4,7-dimethylindenyl)zirconium X_(n),-   bis(indenyl)zirconium X_(n),-   bis(2-methylindenyl)zirconium X_(n),-   cyclopentadienylindenylzirconium X_(n),-   bis(n-propylcyclopentadienyl)hafnium X_(n),-   bis(n-butylcyclopentadienyl)hafnium X_(n),-   bis(n-pentylcyclopentadienyl)hafnium X_(n),-   (n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafnium X_(n),-   bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium X_(n),-   bis(trimethylsilyl cyclopentadienyl)hafnium X_(n),-   bis(2-n-propylindenyl)hafnium X_(n),-   bis(2-n-butylindenyl)hafnium X_(n),-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium X_(n),-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium X_(n),-   bis(9-n-propylfluorenyl)hafnium X_(n),-   bis(9-n-butylfluorenyl)hafnium X_(n),-   (9-n-propylfluorenyl)(2-n-propylindenyl)hafnium X_(n),-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium X_(n),-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   dimethylsilyl(tetramethyleyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   dimethylsilyl(tetramethyleyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium    X_(n),-   dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium,    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium    X_(n),-   methylphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium    X_(n),-   diphenylsilyl(tetramethyleyclopentadienyl)(n-octylamido)titanium    X_(n),-   diphenylsilyl(tetramethyleyclopentadienyl)(n-decylamido)titanium    X_(n),-   diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium    X_(n),    and derivatives thereof.

By “derivatives thereof”, it is meant any substitution or ring formationas described above; and in particular, replacement of the metal “M” (Cr,Zr, Ti or Hf) with an atom selected from the group consisting of Cr, Zr,Hf and Ti; and replacement of the “X” group with any of C₁ to C₅ alkyls,C₆ aryls, C₆ to C₁₀ alkylaryls, fluorine or chlorine; n is 1, 2 or 3.

It is contemplated that the metallocene catalysts components describedabove include their structural or optical or enantiomeric isomers(racemic mixture), and may be a pure enantiomer in one embodiment.

As used herein, a single, bridged, asymmetrically substitutedmetallocene catalyst component having a racemic and/or meso isomer doesnot, itself, constitute at least two different bridged, metallocenecatalyst components.

As mentioned above, the “metallocene catalyst component” may compriseany combination of any “embodiment” described herein.

Phenoxide Transition Metal Catalyst Compositions

Phenoxide transition metal catalyst compositions are heteroatomsubstituted phenoxide ligated Group 3 to 10 transition metal orlanthanide metal compounds wherein the metal is bound to the oxygen ofthe phenoxide group. Phenoxide transition metal catalyst compounds maybe represented by Formula XIV or XV:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably a tertiaryalkyl group, preferably a C₄ to C₂₀ alkyl group, preferably a C₄ to C₂₀tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ group and may ormay not also be bound to M;

at least one of R² to R⁵ is a heteroatom containing group, the rest ofR² to R⁵ are independently hydrogen or a C₁ to C₁₀₀ group, preferably aC₄ to C₂₀ alkyl group, preferred examples of which include butyl,isobutyl, t-butyl, pentyl, hexyl, heptyl, isohexyl, octyl, isooctyl,decyl, nonyl, dodecyl, and any of R² to R⁵ also may or may not be boundto M;

Each R¹ to R⁵ group may be independently substituted or unsubstitutedwith other atoms, including heteroatoms or heteroatom containinggroup(s);

O is oxygen;M is a Group 3 to Group 10 transition metal or lanthanide metal,preferably a Group 4 metal, preferably M is Ti, Zr or Hf;n is the valence state of the metal M, preferably 2, 3, 4, or 5; andQ is, and each Q may be independently be, an alkyl, halogen, benzyl,amide, carboxylate, carbamate, thiolate, hydride or alkoxide group, or abond to an R group containing a heteroatom which may be any of R¹ to R⁵.

A heteroatom containing group may be any heteroatom or a heteroatombound to carbon, silicon or another heteroatom. Preferred heteroatomsinclude boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin,lead, antimony, oxygen, selenium, and tellurium. Particularly preferredheteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even moreparticularly preferred heteroatoms include nitrogen and oxygen. Theheteroatom itself may be directly bound to the phenoxide ring or it maybe bound to another atom or atoms that are bound to the phenoxide ring.The heteroatom containing group may contain one or more of the same ordifferent heteroatoms. Preferred heteroatom containing groups includeimines, amines, oxides, phosphines, ethers, ketones, oxoazolinesheterocyclics, oxazolines, thioethers, and the like. Particularlypreferred heteroatom containing groups include imines. Any two adjacentR groups may form a ring structure, preferably a 5 or 6 membered ring.Likewise the R groups may form multi-ring structures. In one embodimentany two or more R groups do not form a 5 membered ring.

In a preferred embodiment the heteroatom substituted phenoxidetransition metal compound is an iminophenoxide Group 4 transition metalcompound, and more preferably an iminophenoxidezirconium compound.

Supported Catalyst Systems

The mixed catalyst system may further include a support or carrier. Eachcomponent of the mixed catalyst system may be supported on a support orcarrier or each catalyst component may be unsupported. In other words,any one, none, or all of the catalyst components may be supported orunsupported. Further, one of the catalyst components (e.g., thenon-metallocene) may reside on one collection of support particles, andanother catalyst component (e.g., the metallocene) may reside on anothercollection of support particles. The support for each of the individualcomponents may be the same or different.

The term “supported” as used herein refers to one or more compounds thatare deposited on, contacted with, vaporized with, bonded to, orincorporated within, adsorbed or absorbed in, or on, a support orcarrier. The terms “support” or “carrier” for purposes of thisspecification are used interchangeably and are any support material,preferably a porous support material, including inorganic or organicsupport materials. Non-limiting examples of inorganic support materialsinclude inorganic oxides and inorganic chlorides. Other carriers includeresinous support materials such as polystyrene, functionalized orcrosslinked organic supports, such as polystyrene, divinyl benzene,polyolefins, or polymeric compounds, zeolites, talc, clays, or any otherorganic or inorganic support material and the like, or mixtures thereof.

The support materials utilized may be any of the conventional supportmaterials. Preferably the supported material is a porous supportmaterial, for example, talc, inorganic oxides and inorganic chlorides.Other support materials include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds,zeolites, clays, or any other organic or inorganic support material andthe like, or mixtures thereof.

The preferred support materials are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, fumed silica, alumina, silica-alumina and mixtures thereof.Other useful supports include magnesia, titania, zirconia, magnesiumchloride, montmorillonite, phyllosilicate, zeolites, talc, clays and thelike. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania and the like.Additional support materials may include those porous acrylic polymers.Other support materials include nanocomposites, aerogels, spherulites,and polymeric beads. Another support is fumed silica available under thetrade name Cabosil™ TS-610, available from Cabot Corporation. Fumedsilica is typically a silica with particles 7 to 30 nanometers in sizethat has been treated with dimethylsilyldichloride such that a majorityof the surface hydroxyl groups are capped.

In another embodiment, any of the conventionally known inorganic oxides,such as silica, support materials that retain hydroxyl groups afterdehydration treatment methods will be suitable in accordance with theinvention. Because of availability, both of silica and silica containingmetal oxide based supports, for example, silica-alumina, are preferred.Silica particles, gels and glass beads are most typical.

These metal oxide compositions may additionally contain oxides of othermetals, such as those of Al, K, Mg, Na, Si, Ti and Zr and shouldpreferably be treated by thermal and/or chemical means to remove waterand free oxygen. Typically such treatment is in a vacuum in a heatedoven, in a heated fluidized bed or with dehydrating agents such asorgano silanes, siloxanes, alkyl aluminum compounds, etc. The level oftreatment should be such that as much retained moisture and oxygen as ispossible is removed, but that a chemically significant amount ofhydroxyl functionality is retained. Thus calcining at up to 800° C. ormore up to a point prior to decomposition of the support material, forseveral hours is permissible, and if higher loading of supported anionicactivator is desired, lower calcining temperatures for lesser times willbe suitable. Where the metal oxide is silica, loadings to achieve fromless than 0.1 mmol to 3.0 mmol activator/g SiO₂ are typically suitableand can be achieved, for example, by varying the temperature ofcalcining from 200° C. to 1,000° C., such as from 300° C. to 900° C.,400° C. to 875° C., 500° C. to 850° C., 600° C. to 825° C., 700° C. to800° C., and any combination of any limit with any lower limit.

The tailoring of hydroxyl groups available as attachment sites in thisinvention can also be accomplished by the pre-treatment with a less thanstoichiometric amount of a chemical dehydrating agent. If calciningtemperatures below 400° C. are employed, difunctional coupling agents(e.g., (CH₃)₃SiCl₂) may be employed to cap hydrogen bonded pairs ofsilanol groups which are present under the less severe calciningconditions. Similarly, use of the Lewis acid in excess of thestoichiometric amount needed for reaction with the transition metalcompounds will serve to neutralize excess silanol groups withoutsignificant detrimental effect for catalyst preparation or subsequentpolymerization.

In another embodiment, the support is a polymeric support, includinghydroxyl-functional-group-containing polymeric substrates, butfunctional groups may be any of the primary alkyl amines, secondaryalkyl amines, and others, where the groups are structurally incorporatedin a polymeric chain and capable of a acid-base reaction with the Lewisacid such that a ligand filling one coordination site of the aluminum isprotonated and replaced by the polymer incorporated functionality. See,for example, the functional group containing polymers of U.S. Pat. No.5,288,677.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 2001m. Theaverage pore size of the carrier is typically in the range of from 10 to1000 Å, preferably 50 to about 500 Å, and most preferably 75 to about350 Å.

The support materials may be treated chemically, for example with afluoride compound as described in WO 00/12565. Other supportedactivators are described in for example WO 00/13792 that refers tosupported boron containing solid acid complex.

In another embodiment, an antistatic agent or surface modifier that isused in the preparation of the supported catalyst system as described inPCT publication WO 96/11960 may be used with catalyst systems includingthe activator compounds described herein. The catalyst systems may alsobe prepared in the presence of an olefin, for example 1-hexene.

In another embodiment, the activator and/or catalyst system may becombined with a carboxylic acid salt of a metal ester, for examplealuminum carboxylates such as aluminum mono, di- and tri-stearates,aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S.Pat. Nos. 6,300,436 and 6,306,984.

Method For Supporting

Various methods can be used to affix two catalyst components to asupport to form the mixed catalyst system. For example, one procedureincludes forming a mixture (solution or slurry) of the first catalystcomponent and a non-polar hydrocarbon, and contacting this mixture witha mixture (solution or slurry) that includes the second catalystcomponent.

In one aspect, the support is prepared by heating support particles at adehydration temperature of up to 600° C., or to 800° C. or more whenpreparing an “enhanced support,” resulting in a support having amodified chemical structure, e.g., a reduced number of hydroxyl groups.The higher dehydration temperatures are preferred.

The support is preferably an inorganic material such as silicon oxide(silica) or aluminum oxide. The support material can be a dry powder,and in certain embodiments has an average particle size of from 1-500microns, or more narrowly from 10-250 microns. The surface area of thesupport may range from 3 m 2/g to 600 m²/g or more.

A preferred support is an amorphous high surface area silica, such asDavison 952 or Sylopol® 955, sold by Davison Chemical Division of W.R.Grace and Company. Those silicas are in spherical form, prepared by aspray drying process, with a surface area of about 300 m²/g and a porevolume of about 1.65 cm³/g. A procedure for dehydrating the silica at600° C. or more is set forth in U.S. Pat. No. 5,525,678.

A variety of non-polar hydrocarbons can be used to form the supportslurry, but any non-polar hydrocarbon selected should remain in liquidform at all relevant reaction temperatures, and the ingredients used toform the first catalyst component should be at least partially solublein the non-polar hydrocarbon. Accordingly, the non-polar hydrocarbon isconsidered to be a “solvent” herein, even though in certain embodimentsthe ingredients are only partially soluble in the hydrocarbon. Forexample, the organomagnesium compound, alcohol and transition metalcompound of the first catalyst compound, described above, should be atleast partially soluble, and preferably completely soluble, in thathydrocarbon solvent at the mixing temperatures described above.

Examples of suitable non-polar hydrocarbons include C₄-C₁₀ linear orbranched alkanes, cycloalkanes and aromatics. More specifically, anon-polar alkane can be isopentane, hexane, isohexane, n-heptane,octane, nonane, or decane; a non-polar cycloalkane such as cyclohexane;or an aromatic such as benzene, toluene, or ethylbenzene. Mixtures ofdifferent non-polar hydrocarbons can also be used.

The support slurry can be heated both during and after mixing of thesupport particles with the non-polar hydrocarbon solvent, but at thepoint when either or both of the catalysts are combined with the supportslurry, the temperature of the slurry should be sufficiently low so thatneither of the catalysts are inadvertently activated. Thus, thetemperature of the support slurry (e.g., silica slurry) is preferablymaintained at a temperature below 90° C., e.g., from 25 to 70° C., oreven more narrowly from 40 to 60° C.

Activator

The term “activator” as used herein refers to any compound or component,or combination of compounds or components, capable of enhancing theability of a catalyst to polymerize olefin monomers to form polyolefins.In certain embodiments, either or both of the catalyst components may becontacted with a catalyst activator, herein simply referred to as an“activator.”

The activator may be any one or a combination of compounds commonlyemployed to activate Group 15-containing catalysts. These include metalalkyls, hydrides, alkylhydrides, alkylhalides (such as alkyllithiumcompounds), dialkylzinc compounds, trialkylboron compounds,trialkylaluminum compounds, alkylaluminum halides, alkylaluminum andhydrides, and tetraalkylgermanium compounds. Preferably, this activatoris trimethyl aluminum (TMA). The amount of activator is preferablysufficient to give a molar ratio of activator to metal in the catalystcomponent of about 3:1 to about 1000:1, preferably about 15:1 to about300:1, and most preferably about 20:1 to about 100:1.

The activator may also be any one or a combination of compounds suitablefor activating the metal sites of the metallocene type catalyst whichmay be different from the activator described above. This secondactivator is preferably a linear and/or cyclic aluminoxane speciesprepared from the interaction of R₃Al and water, where R is a C₁-C₁₂linear, branched or cyclic alkyl, with the amount of water controllingthe average molecular weight of the aluminoxane molecule. Preferably,methylaluminoxane (MAO) is used.

Polymerization Process

The activators and the polymerization catalysts described above, whethersupported or not, are suitable for use in any prepolymerization and/orpolymerization process over a wide range of temperatures and pressures.The temperatures may be in the range of from −60° C. to about 280° C.,preferably from 50° C. to about 200° C. In one embodiment, thepolymerization temperature is above 0° C., above 50° C., above 80° C.,above 100° C., above 150° C., or above 200° C. In one embodiment, thepressures employed may be in the range from 1 atmosphere to about 500atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase, anda high pressure process, or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefin(s) at least one of which is ethylene or propylene.

In one embodiment, the process is a solution, high pressure, slurry orgas phase polymerization process of one or more olefin monomers havingfrom 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and morepreferably 2 to 8 carbon atoms. The invention is particularly wellsuited to the polymerization of two or more olefin monomers of ethylene,propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octeneand 1-decene.

Other monomers useful include ethylenically unsaturated monomers,diolefins having 4 to 18 carbon atoms, conjugated or nonconjugateddienes, polyenes, vinyl monomers and cyclic olefins. Non-limitingmonomers useful in the invention may include norbornene, norbornadiene,isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkylsubstituted styrene, ethylidene norbornene, dicyclopentadiene andcyclopentene.

In another embodiment, a copolymer of ethylene is produced, where withethylene, a comonomer having at least one alpha-olefin having from 4 to15 carbon atoms, preferably from 4 to 12 carbon atoms, and mostpreferably from 4 to 8 carbon atoms, is polymerized in a gas phaseprocess.

In another embodiment, ethylene or propylene is polymerized with atleast two different comonomers, optionally one of which may be a diene,to form a terpolymer.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms.

Typically in a gas phase polymerization process, a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer.

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment, the reactor temperature in a gas phase process is above 60°C.

Other gas phase processes include series or multistage polymerizationprocesses. Gas phase processes may also include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421.

In another embodiment, the process may produce greater than 500 lbs ofpolymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) orhigher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), morepreferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferablygreater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greaterthan 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greaterthan 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In another embodiment, the slurryprocess temperature is above 100° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In another embodiment, the polymerization technique is referred to as aparticle form polymerization, or a slurry process where the temperatureis kept below the temperature at which the polymer goes into solution.Such technique is well known in the art, and described in for instanceU.S. Pat. No. 3,248,179. Other slurry processes include those employinga loop reactor and those utilizing a plurality of stirred reactors inseries, parallel, or combinations thereof. Non-limiting examples ofslurry processes include continuous loop or stirred tank processes.Also, other examples of slurry processes are described in U.S. Pat. No.4,613,484.

In another embodiment, this process may produce greater than 2000 lbs ofpolymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr(2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540Kg/hr). In another embodiment the slurry reactor may produce greaterthan 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greaterthan 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525.

In one embodiment, the slurry or gas phase process is operated in thepresence of the catalyst system described herein and in the absence ofor essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This process isdescribed in PCT publication WO 96/08520 and U.S. Pat. Nos. 5,712,352and 5,763,543.

In another embodiment, the method provides for injecting the catalystsystem described herein into a reactor, particularly a gas phasereactor. In one embodiment the catalyst system is used in theunsupported form, preferably in a liquid form such as described in U.S.Pat. Nos. 5,317,036 and 5,693,727 and European publication EP-A-0 593083. The polymerization catalyst in liquid form can be fed with anactivator, and/or a support, and/or a supported activator together orseparately to a reactor. The injection methods described in PCTpublication WO 97/46599 may be utilized.

Where an unsupported catalyst system is used the mole ratio of the metalof the activator component to the metal of the catalyst compound is inthe range of between 0.3:1 to 10, 000:1, preferably 100:1 to 5000:1, andmost preferably 500:1 to 2000:1.

Polymer Products

The polymers produced can be used in a wide variety of products andend-use applications. The polymers produced include polyethylenehomopolymers and polyethylene co-polymers, including linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, as well aspolypropylene homopolymers and polypropylene co polymers.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

The polymers produced typically have a molecular weight distribution, aweight average molecular weight to number average molecular weight(M_(w)/M_(n)) of greater than 1.5 to about 15, particularly greater than2 to about 10, more preferably greater than about 2.2 to less than about8, and most preferably from 2.5 to 8. The polymers may have a narrowmolecular weight distribution and a broad composition distribution orvice-versa, and may be those polymers described in U.S. Pat. No.5,798,427.

Also, the polymers typically have a narrow composition distribution asmeasured by Composition Distribution Breadth Index (CDBI). Furtherdetails of determining the CDBI of a copolymer are known to thoseskilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993. The polymers in one embodiment haveCDBI's generally in the range of greater than 50% to 100%, preferably99%, preferably in the range of 55% to 85%, and more preferably 60% to80%, even more preferably greater than 60%, still even more preferablygreater than 65%. In another embodiment, polymers produced using acatalyst system described herein have a CDBI less than 50%, morepreferably less than 40%, and most preferably less than 30%.

The polymers in one embodiment have a melt index (MI) or (I₂) asmeasured by ASTM-D-1238-E (190/2.16) in the range from no measurableflow to 1000 dg/min, more preferably from about 0.01 dg/min to about 100dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min,and most preferably from about 0.1 dg/min to about 10 dg/min.

In one embodiment, the polymers have a melt index ratio (I₂₁/I₂) (I₂₁ ismeasured by ASTM-D-1238-F) (190/21.6) of from 10 to less than 25, morepreferably from about 15 to less than 25. The polymers, in a preferredembodiment, have a melt index ratio (I₂₁/I₂) of from greater than 25,more preferably greater than 30, even more preferably greater that 40,still even more preferably greater than 50 and most preferably greaterthan 65. For example, the melt index ratio (I₂₁/I₂) may be of from 5 to300, 10 to 200, 20 to 180, 30 to 160, 40 to 120, 50 to 100, 60 to 90,and a combination of any upper limit with any lower limit.

Bimodal Polymer Product

The polymers produced by the processes described herein, utilizing themixed catalysts described herein, are preferably bimodal. The term“bimodal,” when used to describe a polymer or polymer composition, e.g.,polyolefins such as polypropylene or polyethylene, or otherhomopolymers, copolymers or terpolymers, means “bimodal molecular weightdistribution,” which term is understood as having the broadestdefinition persons in the pertinent art have given that term asreflected in printed publications and issued patents. For example, asingle composition that includes polyolefins with at least oneidentifiable high molecular weight distribution and polyolefins with atleast one identifiable low molecular weight distribution is consideredto be a “bimodal” polyolefin, as that term is used herein. Preferably,other than having different molecular weights, the high molecular weightpolyolefin and the low molecular weight polyolefin are essentially thesame type of polymer, e.g., polypropylene or polyethylene.

The bimodal polymer products prepared using the mixed catalystsdescribed herein can be used in a wide variety of products and end-useapplications. The polymers produced by the process of the inventioninclude linear low density polyethylene, elastomers, plastomers, highdensity polyethylenes, low density polyethylenes, medium densitypolyethylenes, polypropylene and polypropylene copolymers.

The bimodal polymers that can be made using the described processes canhave a variety of compositions, characteristics and properties. At leastone of the advantages of the catalysts is that the process utilized canbe tailored to form a polymer composition with a desired set ofproperties. For example, it is contemplated that the polymers having thesame properties as the bimodal polymer compositions in U.S. Pat. No.5,525,678 can be formed. Also, the bimetallic catalysts described hereincan be used in polymerization processes to form polymers having the sameproperties as the polymers in the following patents, 6,420,580;6,388,115; 6,380,328; 6,359,072; 6,346,586; 6,340,730; 6,339,134;6,300,436; 6,274,684; 6,271,323; 6,248,845; 6,245,868; 6,245,705;6,242,545; 6,211,105; 6,207,606; 6,180,735; and 6,147,173.

The bimodal polymers, typically ethylene based polymers, should have adensity in the range of from 0.86 g/cc to 0.97 g/cc, preferably in therange of from 0.88 g/cc to 0.965 g/cc, more preferably in the range offrom 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from0.905 g/cc to 0.955 g/cc, yet even more preferably in the range from0.910 g/cc to 0.955 g/cc, and most preferably greater than 0.915 g/cc,preferably greater than 0.920 g/cc, and most preferably greater than0.925 g/cc.

The bimodal polymers can have a molecular weight distribution, a weightaverage molecular weight to number average molecular weight(M_(w)/M_(n)) of greater than 5 to about 80, particularly greater than10 to about 60, more preferably greater than about 15 to less than about55, and most preferably from 20 to 50.

The bimodal polymers made by the described processes can in certainembodiments have a melt index (MI) or (I₂) as measured by ASTM-D-1238-Ein the range from 0.01 dg/min to 1000 dg/min, more preferably from about0.01 dg/min to about 100 dg/min, even more preferably from about 0.02dg/min to about 50 dg/min, and most preferably from about 0.03 dg/min toabout 0.1 dg/min.

The bimodal polymers made by the described processes can in certainembodiments have a melt index ratio (I₂₁/I₂) (I₂₁ is measured byASTM-D-1238-F) of from 40 to less than 500, more preferably from about60 to less than 200.

Expressed differently, bimodal polymers made by the described processescan in certain embodiments have a melt index ratio (I₂₁/I₂) (I₂₁ ismeasured by ASTM-D-1238-F) of from preferably greater than 40, morepreferably greater than 50, even more preferably greater that 60, stilleven more preferably greater than 65 and most preferably greater than70. In one or more other embodiments, the polymer of the invention mayhave a narrow molecular weight distribution and a broad compositiondistribution or vice-versa, and may be those polymers described in U.S.Pat. No. 5,798,427.

In certain embodiments, propylene based polymers can be produced usingthe processes described herein. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene-type catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, pipe and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, geomembranes,and pond liners. Molded articles include single and multi-layeredconstructions in the form of bottles, tanks, large hollow articles,rigid food containers and toys, etc.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific embodiments of the present invention, theyare not to be viewed as limiting the invention in any specific respect.All parts, proportions, and percentages are by weight unless otherwiseindicated. All examples were carried out in dry, oxygen-freeenvironments and solvents. All molecular weights are weight averagemolecular weight unless otherwise noted. Molecular weights (weightaverage molecular weight (M_(w)) and number average molecular weight(M_(n)) and (M_(z)) were measured by Gel Permeation Chromatography(GPC).

General Procedure for Synthesis

The catalyst synthesis and preparation is described below. Allmanipulations, unless otherwise noted, were performed in anitrogen-filled glove box or using standard Schlenk techniques, unlessstated otherwise. The reagents, particularly toluene and hexane werepassed through individual sets of one gallon cylinders containing 13Xmolecular sieves and de-oxo catalyst before use. Deuterated benzene andtoluene were dried over NaK alloy. Deuterated benzene, toluene, andtetrahydrofuran were degassed by the freeze-pump-thaw method. (Thedeuterated tetrahydrofuran was dried over sodium.) MOS (silica-supportedMAO, 4.5 mmol Al/g) was obtained from Exxon. Kaydol mineral oil waspurged with nitrogen while heated to 200° C. All other reagents wereused as received from Aldrich.

In situ reagents were identified by comparison of starting reagents incomparable deuterated solvents. Quantitative internal standards for ¹HNMR spectra were referenced to protio impurities in the deuteriosolvents. ¹⁹F NMR spectra were referenced to −76.55 ppm CF₃COOH externalstandard solution. ¹H NMR spectra were obtained from a QE-300 (¹H, 300MHz) at room temperature.

1. Synthesis of “HN3” {(HN(CH₂CH₂NHMesityl)₂)}

In dry box, a one liter Schlenk flask equipped with a stirbar wascharged with, in the following order, 200 mL of toluene, diethyltriamine(12.31 mL, 114 mmol) bromomesitylene (34.8 mL, 227 mmol), Pd(II) dba(0.523 g, 0.571 mmol), rac-BINAP (1.064 g, 1.7 mmol), Na t-butoxide(32.8 g, 340 mmol), and 200 mL toluene (400 mL toluene total). On aSchlenk line with an argon atmosphere, the dark red heterogeneoussolution was equipped with a reflux condenser and heated at 102° C. inan oil bath. After 19 hours, the reaction was removed from the oil bathand allowed to cool to room temperature. The wine colored heterogeneoussolution was then transferred to a 2 liter separatory funnel anddissolved in 750 mL ether. The ether solution was washed with water(2×250 mL) and brine (2×250 mL) and then dried over magnesium sulfate.Solvent was removed in vacuo on rotovap. The yellow/amber oil was thenplaced on Schlenk line and left under vacuum overnight. When the flaskwas returned to normal atmosphere pressure, the oil turned to clumps. ¹HNMR confirmed the isolation of the desired product as yellow/ambersolids (38.2 g, 98.7% yield). ¹H NMR (C₆D₆): δ 0.73 (br s, 1H), 2.21 (s,3H), 2.27 (s, 6H), 2.50 (t, 2H), 2.85 (t, 3H), 3.37 (br s, 1H), 6.83 (brs, 2H).

2. Synthesis of HN5“{(HN(CH₂CH₂NHC₆(CH₃)₅)₂)}”

In dry box, a one liter Schlenk flask equipped with a stirbar wascharged with, in the following order, 200 mL of toluene, Pd(II) dba(0.507 g, 0.553 mmol), rac-BINAP (1.05 g, 1.69 mmol), diethyltriamine(11.36 mL, 110 mmol) bromopentamethylbenzene, (50 g, 220 mmol), Nat-butoxide (31.73 g, 330 mmol), and 200 mL toluene (400 mL toluenetotal). On a Schlenk line with an argon atmosphere, the dark redheterogeneous solution was equipped with a reflux condenser and heatedat 100° C. in an oil bath. After 19 hours, the reaction was removed fromthe oil bath and allowed to cool to room temperature. The wine coloredheterogeneous solution was then transferred to a 2 liter separatoryfunnel and dissolved in 750 mL ether. The ether solution was washed withwater (2×250 mL) and brine (2×250 mL) and then dried over magnesiumsulfate. Solvent was removed in vacuo on rotovap. The yellow/amber oilwas then placed on Schlenk line and left under vacuum overnight. Whenthe flask was returned to normal atmosphere pressure, the oil turned toclumps. ¹H NMR confirmed the isolation of the desired product as yellowsolids (35.3 g, 86%). ¹H-NMR (C₆D₆): δ 0.88 (br s, 1H), 2.14 (s, 3H),2.150 (s, 6H), 2.32 (s, 6H), 2.62 (t, 2H), 2.87 (t, 2H), 3.47 (br s,1H).

3. Synthesis of HN3Zr(NMe₂)₂

To a 50 mL flask, 7 mL of hexane was added to 1.267 g (3.737 mmol) of(1) HN3 and allowed to stir for ten minutes.Tetrakis(dimethylamino)zirconium (1.00 g, 3.737 mmol) was added to theslurry and left to stir for two hours. Volatiles were removed by vacuumfrom the heterogeneous amber slurry resulting in the isolation of 1.81 g(94%) of a tan precipitate. ¹H NMR (C₆D₆): δ 1.80 (m, 1H), 2.21 (s, 6H),2.28 (s, 6H), 2.45 (s, 6H), 2.47 (s, 6H), 2.59 (m, 4H), 3.00 (m, 2H),3.05 (s, 6H), 3.35 (s, 2H), 6.95 (br s, 4H).

4. Synthesis of C₆F₅OSi(CH₃)₃

n-Butyllithium (9.75 mL, 22.39 mmol, 2.5 M in hexane) was addeddropwise, at 0° C., to a 200 mL hexane solution of C₆F₅OH (4.08 g, 22.17mmol). After the addition of n-butyllithium was complete, the reactionmixture was allowed to warm to room temperature. Chlorotrimethylsilane(2.65 g, 24.39 mmol) was added to the reaction at −40° C. After slowlywarming to room temperature, the reaction was refluxed for 19 hours.Isolation of the crude product was achieved by ether extraction. Theorganic was washed with ammonium chloride, water, brine, and dried oversodium sulfate. Solvent was removed in vacuo to yield 4.0 g of crudeproduct. The resulting liquid was purified by vacuum distillation togive 3.4 g (60%) of a colorless liquid. ¹H NMR(C6D6): δ 0.081 (br. s).

5. Synthesis of HN5Zr(NMe₂)₂

100 mL of hexane was added to 3.00 g (11.21 mmol) of (2) HN5 and allowedto stir for ten minutes. Tetrakis(dimethylamino)zirconium (4.43 g, 11.21mmol) was added to the slurry and left to stir for 19 hours. Theheterogeneous solution was concentrated to half volume. The resultingtan precipitate was isolated by filtration and the remaining volatileswere removed by vacuum. Total yield of desired product was 5.14 g (80%).¹H NMR (C₆D₆): δ 1.85 (br m, 1H), 2.14 (s, 6H), 2.20 (s, 6H), 2.22 (s,6H), 2.24 (s, 6H), 2.50 (s, 6H), 2.53 (s, 6H), 2.68 (m, 4H), 3.04 (m,2H), 3.12 (s, 6H), 3.37 (m, 2H).

Example 1 HN3Zr(OC₆F₅)₂

9 mL of a 0.05 M stock solution of (3) HN3Zr(NMe₂)₂ was added to 0.346 g(1.35 mmol) of (4) C₆F₅OSi(CH₃)₃ and allowed to stir at room temperaturefor three days. Volatiles were removed in vacuo from the homogeneouslight amber solution leaving a tan sticky paste in the reaction flask.Triturations with hexane resulted in 0.559 g of a crude white solid.When these solids were dissolved in C₆D₆ for ¹H NMR analysis, 0.032 gprecipitated out of solution and 23.9 mg (9% yield) of the desiredproduct was isolated. The kinetic parameters are listed in Table 5below. ¹H NMR (C₆D₆): δ 2.04 (s, 6H), 2.19 (s, 6H), 2.63 (s, 6H), 2.60(br m, 4H), 2.82 (m, 2H), 3.33 (m, 2H), 6.70 (s, 2H), 6.73 (s, 2H).

Examples 2 and 3 HN5Zr(NMe₂)(OC₆F₅) and HN5Zr(OC₆F₅)₂

0.600 g (1.047 mmol) of (5) HN5Zr(NMe₂)₂ was slowly added to a flaskcharged with 2.3 g (8.97 mmol) of (4) C₆F₅OSi(CH₃)₃ and the amber yellowheterogeneous solution (solution was initially heterogeneous lightyellow) was allowed to stir for 2 hours. An equivalent volume of hexanewas added to the reaction flask and the hexane insoluble solids wereisolated as a tan powder (0.132 g) which, by ¹H NMR (C₆D₆) analysis, wasthe mono substituted product. After 26 days, crystals were observed inthe hexane wash and isolated (0.212 g, 29% yield) by decanting away theliquid and drying by vacuum.

A proton NMR study revealed that the crystal contained the followingmolecules:

[(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂ and

[(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂(NMe₂H)

¹H NMR (C₆D₆): δ 2.05 (s, 6H), 2.16 (s, 6H), 2.17 (s, 6H), 2.32 (s, 6H),2.49 (s, 6H), 2.62 (m, 5H), 2.94 (s, 6H), 2.98 (m, 2H), 3.33 (m, 2H).

¹H NMR (C₆D₆): δ 1.97 (s, 6H), 2.02 (s, 6H), 2.12 (s, 6H), 2.19 (s, 6H),2.42 (s, 6H), 2.72 (br m, 5H), 2.92 (br m, 2H), 3.40 (br m, 2H).

A crystallography of the crystals was also performed. A colorlesscrystal of dimensions 0.32×0.38×0.45 mm was covered in theperfluoropolyether PFO-XR75 (Lancaster) and sealed under nitrogen in aglass capillary. The crystal was optically aligned on the four-circle ofa Siemens P4 diffractometer equipped with a graphite monochromaticcrystal, a MoKα radiation source (λ=0.71073 Å), and a SMART CCD detectorheld at 5.054 cm from the crystal. The sample was cooled to −50° C. witha nitrogen stream produced by a LT-2 low temperature system. Four setsof 20 frames each were collected using the ω scan method with a tensecond exposure time. Integration of these frames followed by reflectionindexing and least squares refinement produced a crystal orientationmatrix for the triclinic lattice.

Data collection consisted of the measurement of a total of 1650 framesin five different runs covering a hemisphere of data. All 1650crystallographic raw data frames were read by program SAINT (version5/6.0)¹ and integrated using 3D profiling algorithms. The resulting datawere reduced to produce a total of 27825 reflections and theirintensities and estimated standard deviations. An absorption correctionwas applied using the SADABS routine available in SAINT. The data werecorrected for Lorentz and polarization effects as well as any crystaldecay. The unit cell parameters, based upon the refinement of 8512reflections, are a=13.9403(8) Å, b=15.4456(8) Å, c=18.8204(11) Å,α=91.580(1)°, β=107.242(1)°, γ=93.358(1)°, and V=3859.3(4) Å³. Datapreparation was carried out by using the program XPREP,¹ which gave17246 unique reflections (R_(int)=2.84%) with indices −17≦h≦18,−20≦k≦19, −21≦1≦24. The space group was determined to be P(−1) (No. 2).

The structure was solved by a combination of direct methods and Fouriermethods with the use of SHELXTL6.1. There are two different molecules inthe crystallographic asymmetric unit. One compound is thefive-coordinate complex [(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂ andthe other is its six-coordinate dimethylamine adduct[(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(Oc₆F₅)₂(NMe₂H). The positions for thehydrogen atoms bound to N(2), N(5), and N(7) were refined with theirisotropic temperature factors set at 1.2 times that of the respectivenitrogen atom. Idealized positions for the remaining hydrogen atoms wereincluded as fixed contributions using a riding model with isotropictemperature factors set at 1.2 (aromatic protons) or 1.5 (methylprotons) times that of the adjacent carbon atom. The positions of themethyl hydrogens were optimized by a rigid rotating group refinementwith idealized tetrahedral angles. Full-matrix least-squares refinement,based upon the minimization of εw_(i) |F_(o) ²−F_(c) ²|², with w_(i)⁻¹=[σ² (F_(o) ²)+(0.0601 P)²+0.1887 P], where P=(Max(F_(o) ², 0)+2 F_(c)²)/3, converged to give final discrepancy indices of R1=0.0446,wR2=0.1157 for 12456 reflections with I>2σ(I). The goodness of fit (GOF)value was 1.075.

A correction for secondary extinction was not applied. The maximum andminimum residual electron density peaks in the final difference Fouriermap were 0.567 and −0.833 e/Å³, respectively. The linear absorptioncoefficient, atomic scattering factors and anomalous dispersioncorrections were calculated from values from the International Tablesfor X-ray Crystallography.

FIG. 1 shows an ORTEP of [(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂.FIG. 2 shows an ORTEP of[(C₆Me₅)NCH₂CH₂NHCH₂CH₂N(C₆Me₅)]Zr(OC₆F₅)₂(NMe₂H). Atomic Coordinatesfor Nonhydrogen Atoms and equivalent isotropic displacement parametersare listed in Table 1. Table 2 lists the interatomic distances [Å] andbond angles [°]. Table 3 lists the anisotropic displacement parameters[A²×10³]. Table 4 lists the hydrogen atom coordinates (×10⁴) andisotropic displacement parameters.

TABLE 1 Atomic coordinates [×10⁴] and equivalent isotropic displacementparameters [A² × 10³]. U(eq) is defined as one third of the trace of theorthogonalized U_(ij) tensor. x y z U(eq) Zr(1) 3424(1) 9082(1) 1698(1)36(1) O(1) 4091(2) 7987(1) 2009(1) 48(1) O(2) 1969(2) 8740(1) 1175(1)58(1) N(1) 3616(2) 9800(1) 2661(1) 41(1) N(2) 3150(2) 10551(1)  1399(1)50(1) N(3) 4241(2) 9425(1)  999(1) 43(1) F(1) 3014(1) 6846(1)  896(1)72(1) F(2) 3759(2) 5359(1)  607(2) 112(1)  F(3) 5645(2) 4983(1) 1409(2)123(1)  F(4) 6757(2) 6115(1) 2496(2) 109(1)  F(5) 6014(2) 7597(1)2804(1) 83(1) F(6)  706(2) 10059(2)  1059(1) 97(1) F(7) −1287(2) 9785(2)  351(2) 104(1)  F(8) −2069(1)  8185(1) −258(1) 81(1) F(9)−843(2) 6862(1) −153(2) 97(1) F(10) 1142(2) 7143(1)  519(2) 97(1) C(1)3529(3) 10738(2)  2733(2) 54(1) C(2) 2879(3) 11017(2)  1994(2) 58(1)C(3) 4078(3) 10920(2)  1267(2) 58(1) C(4) 4357(3) 10307(2)   742(2)60(1) C(5) 3841(2) 9377(2) 3358(1) 42(1) C(6) 3047(2) 9030(2) 3595(2)49(1) C(7) 3280(3) 8617(2) 4279(2) 57(1) C(8) 4267(3) 8554(2) 4702(2)58(1) C(9) 5052(2) 8909(2) 4465(2) 52(1) C(10) 4845(2) 9329(2) 3788(2)43(1) C(11) 1971(2) 9100(2) 3135(2) 66(1) C(12) 2407(3) 8244(3) 4539(2)90(1) C(13) 4509(3) 8091(3) 5429(2) 84(1) C(14) 6140(3) 8860(2) 4922(2)74(1) C(15) 5684(2) 9715(2) 3528(2) 55(1) C(16) 4707(2) 8777(2)  681(1)39(1) C(17) 5719(2) 8627(2) 1036(1) 44(1) C(18) 6148(2) 7940(2)  778(2)50(1) C(19) 5595(2) 7433(2)  149(2) 51(1) C(20) 4615(2) 7616(2) −226(2)49(1) C(21) 4159(2) 8284(2)  41(2) 43(1) C(22) 6321(2) 9208(2) 1690(2)65(1) C(23) 7226(3) 7761(3) 1201(2) 79(1) C(24) 6054(3) 6670(2) −121(2)79(1) C(25) 4021(3) 7101(3) −927(2) 85(1) C(26) 3082(2) 8478(2) −356(2)62(1) C(27) 4472(2) 7255(2) 1866(2) 44(1) C(28) 3937(2) 6665(2) 1308(2)52(1) C(29) 4307(3) 5906(2) 1155(2) 66(1) C(30) 5267(3) 5725(2) 1556(2)74(1) C(31) 5815(3) 6291(2) 2105(2) 69(1) C(32) 5428(2) 7044(2) 2262(2)56(1) C(33)  989(2) 8598(2)  838(2) 51(1) C(34)  331(3) 9256(2)  776(2)64(1) C(35) −682(3) 9115(3)  421(2) 70(1) C(36) −1076(2)  8313(2) 108(2) 62(1) C(37) −457(2) 7656(2)  168(2) 62(1) C(38)  556(2) 7799(2) 523(2) 60(1) Zr(2)  438(1) 4767(1) 2678(1) 37(1) O(3) −180(2) 5756(1)3075(1) 56(1) O(4)  875(2) 3616(1) 3126(1) 60(1) N(4) 1540(2) 5085(1)2171(1) 44(1) N(5) −282(2) 5492(2) 1560(1) 50(1) N(6) −861(2) 4049(1)2025(1) 44(1) N(7) 1751(2) 5209(2) 3908(1) 51(1) F(11) −1329(2)  5685(1)4037(1) 73(1) F(12) −2241(2)  7082(2) 4317(1) 85(1) F(13) −1995(2) 8607(1) 3695(1) 96(1) F(14) −838(2) 8703(1) 2750(1) 94(1) F(15)  27(2)7299(1) 2432(1) 77(1) F(16) −270(2) 3864(1) 4041(1) 84(1) F(17) −657(2)2578(2) 4881(1) 100(1)  F(18)  180(2) 1040(2) 4879(1) 105(1)  F(19)1411(2)  806(1) 4025(1) 101(1)  F(20) 1769(2) 2066(1) 3163(1) 83(1)C(39) 1346(3) 5377(2) 1404(2) 63(1) C(40)  241(2) 5226(2) 1030(2) 59(1)C(41) −1378(2)  5305(2) 1306(2) 61(1) C(42) −1584(2)  4343(2) 1347(2)61(1) C(43) 2607(2) 5087(2) 2532(2) 44(1) C(44) 3096(2) 4331(2) 2479(2)47(1) C(45) 4105(2) 4302(2) 2870(2) 60(1) C(46) 4627(2) 5025(3) 3315(2)70(1) C(47) 4151(3) 5794(2) 3331(2) 65(1) C(48) 3147(2) 5828(2) 2928(2)52(1) C(49) 2519(3) 3558(2) 2003(2) 62(1) C(50) 4621(3) 3472(3) 2822(3)95(1) C(51) 5734(3) 4975(4) 3779(3) 126(2)  C(52) 4708(3) 6585(3)3809(3) 109(2)  C(53) 2621(3) 6667(2) 2916(2) 70(1) C(54) −1215(2) 3220(2) 2221(1) 40(1) C(55) −1898(2)  3185(2) 2632(2) 43(1) C(56)−2177(2)  2383(2) 2873(2) 45(1) C(57) −1756(2)  1632(2) 2721(2) 48(1)C(58) −1110(2)  1661(2) 2281(2) 48(1) C(59) −851(2) 2450(2) 2013(2)45(1) C(60) −2326(2)  4004(2) 2824(2) 57(1) C(61) −2917(3)  2347(2)3317(2) 69(1) C(62) −1998(3)   780(2) 3046(2) 70(1) C(63) −677(3) 843(2) 2091(2) 75(1) C(64) −178(3) 2489(2) 1517(2) 62(1) C(65) −618(2)6442(2) 3223(2) 50(1) C(66) −1202(2)  6424(2) 3708(2) 53(1) C(67)−1668(2)  7141(2) 3861(2) 61(1) C(68) −1551(3)  7909(2) 3542(2) 65(1)C(69) −974(3) 7954(2) 3075(2) 65(1) C(70) −523(2) 7236(2) 2913(2) 56(1)C(71)  732(2) 2999(2) 3563(2) 45(1) C(72) 1172(2) 2210(2) 3589(2) 51(1)C(73)  990(3) 1568(2) 4026(2) 61(1) C(74)  371(3) 1671(2) 4459(2) 64(1)C(75)  −53(2) 2452(2) 4460(2) 63(1) C(76)  141(2) 3093(2) 4027(2) 52(1)C(77) 2489(3) 4572(2) 4241(2) 66(1) C(78) 1420(3) 5634(2) 4496(2) 72(1)

TABLE 2 Interatomic distances [Å] and bond angles [°]. Zr(1)—O(1)1.9951(16) Zr(1)—O(2) 2.006(2) Zr(1)—N(1) 2.039(2) Zr(1)—N(3) 2.040(2)Zr(1)—N(2) 2.377(2) O(1)—C(27) 1.332(3) O(2)—C(33) 1.327(3) N(1)—C(5)1.439(3) N(1)—C(1) 1.466(3) N(2)—C(2) 1.468(4) N(2)—C(3) 1.474(4)N(3)—C(16) 1.434(3) N(3)—C(4) 1.474(3) F(1)—C(28) 1.340(3) F(2)—C(29)1.331(4) F(3)—C(30) 1.346(3) F(4)—C(31) 1.349(4) F(5)—C(32) 1.347(3)F(6)—C(34) 1.347(4) F(7)—C(35) 1.357(4) F(8)—C(36) 1.351(4) F(9)—C(37)1.359(4) F(10)—C(38) 1.340(4) C(1)—C(2) 1.508(4) C(3)—C(4) 1.498(4)C(5)—C(6) 1.397(4) C(5)—C(10) 1.401(4) (6)-C(7) 1.411(4) C(6)—C(11)1.504(4) (7)-C(8) 1.381(5) C(7)—C(12) 1.530(5) (8)-C(9) 1.390(5)C(8)—C(13) 1.519(4) (9)-C(10) 1.406(4) C(9)—C(14) 1.513(4) (10)-C(15)1.495(4) C(16)—C(21) 1.396(4) (16)-C(17) 1.407(4) C(17)—C(18) 1.392(4)(17)-C(22) 1.505(4) C(18)—C(19) 1.396(4) C(18)—C(23) 1.523(4)C(19)—C(20) 1.389(4) C(19)—C(24) 1.517(4) C(20)—C(21) 1.400(4)C(20)—C(25) 1.508(4) C(21)—C(26) 1.517(4) C(27)—C(28) 1.376(4)C(27)—C(32) 1.382(4) C(28)—C(29) 1.365(4) C(29)—C(30) 1.377(5)C(30)—C(31) 1.347(5) C(31)—C(32) 1.372(4) C(33)—C(38) 1.377(4)C(33)—C(34) 1.393(4) C(34)—C(35) 1.374(5) C(35)—C(36) 1.369(5)C(36)—C(37) 1.356(4) C(37)—C(38) 1.374(4) Zr(2)—O(3) 2.0274(18)Zr(2)—O(4) 2.0371(17) Zr(2)—N(4) 2.078(2) Zr(2)—N(6) 2.095(2) Zr(2)—N(5)2.387(2) Zr(2)—N(7) 2.537(2) O(3)—C(65) 1.316(3) O(4)—C(71) 1.319(3)N(4)—C(43) 1.440(3) N(4)—C(39) 1.477(3) N(5)—C(40) 1.463(4) N(5)—C(41)1.467(4) N(6)—C(54) 1.442(3) N(6)—C(42) 1.473(3) N(7)—C(78) 1.471(4)N(7)—C(77) 1.480(4) F(11)—C(66) 1.341(3) F(12)—C(67) 1.336(4)F(13)—C(68) 1.340(3) F(14)—C(69) 1.354(4) F(15)—C(70) 1.351(4)F(16)—C(76) 1.354(3) F(17)—C(75) 1.333(4) F(18)—C(74) 1.336(3)F(19)—C(73) 1.346(3) F(20)—C(72) 1.339(3) C(39)—C(40) 1.493(4)C(41)—C(42) 1.505(4) C(43)—C(48) 1.396(4) C(43)—C(44) 1.402(4)C(44)—C(45) 1.385(4) C(44)—C(49) 1.509(4) C(45)—C(46) 1.403(5)C(45)—C(50) 1.519(4) C(46)—C(47) 1.397(5) C(46)—C(51) 1.539(5)C(47)—C(48) 1.385(5) C(47)—C(52) 1.524(5) C(48)—C(53) 1.523(4)C(54)—C(55) 1.393(4) C(54)—C(59) 1.409(4) C(55)—C(56) 1.404(4)C(55)—C(60) 1.509(4) C(56)—C(57) 1.391(4) C(56)—C(61) 1.506(4)C(57)—C(58) 1.392(4) (57)-C(62) 1.527(4) C(58)—C(59) 1.400(4) (58)-C(63)1.510(4) C(59)—C(64) 1.507(4) (65)-C(70) 1.388(4) C(65)—C(66) 1.391(4)(66)-C(67) 1.383(4) C(67)—C(68) 1.367(5) (68)-C(69) 1.357(5) C(69)—C(70)1.375(4) (71)-C(76) 1.375(4) C(71)—C(72) 1.392(3) (72)-C(73) 1.364(4)C(73)—C(74) 1.364(5) C(74)—C(75) 1.375(5) C(75)—C(76) 1.366(4)O(1)—Zr(1)—O(2) 106.74(8) O(1)—Zr(1)—N(1) 105.34(8) O(2)—Zr(1)—N(1)112.22(9) O(1)—Zr(1)—N(3) 96.10(8) O(2)—Zr(1)—N(3) 113.98(9)N(1)—Zr(1)—N(3) 119.81(9) O(1)—Zr(1)—N(2) 162.46(9) O(2)—Zr(1)—N(2)90.12(9) N(1)—Zr(1)—N(2) 71.50(8) N(3)—Zr(1)—N(2) 72.02(9)C(27)—O(1)—Zr(1) 152.21(18) C(33)—O(2)—Zr(1) 174.2(2) C(5)—N(1)—C(1)113.8(2) C(5)—N(1)—Zr(1) 119.56(15) C(1)—N(1)—Zr(1) 126.61(17)C(2)—N(2)—C(3) 113.7(3) C(2)—N(2)—Zr(1) 110.47(17) C(3)—N(2)—Zr(1)106.46(16) C(16)—N(3)—C(4) 114.6(2) C(16)—N(3)—Zr(1) 120.15(15)C(4)—N(3)—Zr(1) 125.12(18) N(1)—C(1)—C(2) 107.5(2) N(2)—C(2)—C(1)108.4(2) N(2)—C(3)—C(4) 108.1(3) N(3)—C(4)—C(3) 106.9(2) C(6)—C(5)—C(10)121.3(2) C(6)—C(5)—N(1) 118.9(2) C(10)—C(5)—N(1) 119.8(2) C(5)—C(6)—C(7)118.2(3) C(5)—C(6)—C(11) 120.8(3) C(7)—C(6)—C(11) 121.0(3)C(8)—C(7)—C(6) 121.0(3) C(8)—C(7)—C(12) 121.0(3) C(6)—C(7)—C(12)118.0(3) C(7)—C(8)—C(9) 120.4(3) C(7)—C(8)—C(13) 120.5(3)C(9)—C(8)—C(13) 119.1(3) C(8)—C(9)—C(10) 120.0(3) C(8)—C(9)—C(14)121.5(3) C(10)—C(9)—C(14) 118.5(3) C(5)—C(10)—C(9) 119.1(3)C(5)—C(10)—C(15) 120.4(2) C(9)—C(10)—C(15) 120.5(3) C(21)—C(16)—C(17)120.3(2) C(21)—C(16)—N(3) 120.7(2) C(17)—C(16)—N(3) 118.9(2)C(18)—C(17)—C(16) 119.4(2) C(18)—C(17)—C(22) 120.9(3) C(16)—C(17)—C(22)119.6(3) C(17)—C(18)—C(19) 120.2(3) C(17)—C(18)—C(23) 118.3(3)C(19)—C(18)—C(23) 121.5(3) C(20)—C(19)—C(18) 120.1(3) C(20)—C(19)—C(24)119.7(3) C(18)—C(19)—C(24) 120.2(3) C(19)—C(20)—C(21) 120.4(3)C(19)—C(20)—C(25) 120.9(3) C(21)—C(20)—C(25) 118.7(3) C(16)—C(21)—C(20)119.3(2) C(16)—C(21)—C(26) 119.8(3) C(20)—C(21)—C(26) 120.8(3)O(1)—C(27)—C(28) 121.6(2) O(1)—C(27)—C(32) 122.3(3) C(28)—C(27)—C(32)116.1(2) F(1)—C(28)—C(29) 118.7(3) F(1)—C(28)—C(27) 118.5(2)C(29)—C(28)—C(27) 122.7(3) F(2)—C(29)—C(28) 120.4(3) F(2)—C(29)—C(30)120.2(3) C(28)—C(29)—C(30) 119.4(3) F(3)—C(30)—C(31) 120.5(3)F(3)—C(30)—C(29) 120.1(3) C(31)—C(30)—C(29) 119.4(3) C(30)—C(31)—F(4)119.4(3) C(30)—C(31)—C(32) 120.6(3) F(4)—C(31)—C(32) 119.9(3)F(5)—C(32)—C(31) 118.3(3) F(5)—C(32)—C(27) 119.9(2) C(31)—C(32)—C(27)121.7(3) O(2)—C(33)—C(38) 122.6(3) O(2)—C(33)—C(34) 121.7(3)C(38)—C(33)—C(34) 115.7(3) F(6)—C(34)—C(35) 119.2(3) F(6)—C(34)—C(33)118.9(3) C(35)—C(34)—C(33) 121.9(3) F(7)—C(35)—C(36) 119.9(3)F(7)—C(35)—C(34) 119.8(4) C(36)—C(35)—C(34) 120.3(3) F(8)—C(36)—C(37)120.9(3) F(8)—C(36)—C(35) 120.0(3) C(37)—C(36)—C(35) 119.2(3)C(36)—C(37)—F(9) 119.3(3) C(36)—C(37)—C(38) 120.4(3) F(9)—C(37)—C(38)120.3(3) F(10)—C(38)—C(37) 117.7(3) F(10)—C(38)—C(33) 119.6(3)C(37)—C(38)—C(33) 122.5(3) O(3)—Zr(2)—O(4) 130.31(9) O(3)—Zr(2)—N(4)117.59(9) O(4)—Zr(2)—N(4) 101.88(9) O(3)—Zr(2)—N(6) 100.70(9)O(4)—Zr(2)—N(6) 85.67(8) N(4)—Zr(2)—N(6) 116.89(9) O(3)—Zr(2)—N(5)79.28(8) O(4)—Zr(2)—N(5) 145.83(9) N(4)—Zr(2)—N(5) 70.28(8)N(6)—Zr(2)—N(5) 70.22(8) O(3)—Zr(2)—N(7) 77.11(8) O(4)—Zr(2)—N(7)76.07(8) N(4)—Zr(2)—N(7) 86.99(9) N(6)—Zr(2)—N(7) 152.73(8)N(5)—Zr(2)—N(7) 134.24(8) C(65)—O(3)—Zr(2) 170.69(19) C(71)—O(4)—Zr(2)146.6(2) C(43)—N(4)—C(39) 110.4(2) C(43)—N(4)—Zr(2) 124.57(16)C(39)—N(4)—Zr(2) 125.03(19) C(40)—N(5)—C(41) 114.9(3) C(40)—N(5)—Zr(2)106.61(16) C(41)—N(5)—Zr(2) 110.03(17) C(54)—N(6)—C(42) 110.5(2)C(54)—N(6)—Zr(2) 123.71(15) C(42)—N(6)—Zr(2) 125.55(17) C(78)—N(7)—C(77)109.5(3) C(78)—N(7)—Zr(2) 118.3(2) C(77)—N(7)—Zr(2) 117.41(19)N(4)—C(39)—C(40) 107.1(2) N(5)—C(40)—C(39) 107.8(3) N(5)—C(41)—C(42)107.7(2) N(6)—C(42)—C(41) 108.5(2) C(48)—C(43)—C(44) 120.5(3)C(48)—C(43)—N(4) 120.7(2) C(44)—C(43)—N(4) 118.8(2) C(45)—C(44)—C(43)119.4(3) C(45)—C(44)—C(49) 120.8(3) C(43)—C(44)—C(49) 119.9(3)C(44)—C(45)—C(46) 119.9(3) C(44)—C(45)—C(50) 118.9(3) C(46)—C(45)—C(50)121.2(3) C(47)—C(46)—C(45) 120.4(3) C(47)—C(46)—C(51) 119.9(4)C(45)—C(46)—C(51) 119.8(4) C(48)—C(47)—C(46) 119.6(3) C(48)—C(47)—C(52)119.4(3) C(46)—C(47)—C(52) 121.0(4) C(47)—C(48)—C(43) 119.9(3)C(47)—C(48)—C(53) 120.5(3) C(43)—C(48)—C(53) 119.5(3) C(55)—C(54)—C(59)120.3(2) C(55)—C(54)—N(6) 119.8(2) C(59)—C(54)—N(6) 120.0(2)C(54)—C(55)—C(56) 119.4(2) C(54)—C(55)—C(60) 120.3(2) C(56)—C(55)—C(60)120.2(3) C(57)—C(56)—C(55) 120.4(3) C(57)—C(56)—C(61) 120.2(3)C(55)—C(56)—C(61) 119.4(3) C(56)—C(57)—C(58) 120.0(2) C(56)—C(57)—C(62)119.6(3) C(58)—C(57)—C(62) 120.4(3) C(57)—C(58)—C(59) 120.3(2)C(57)—C(58)—C(63) 120.4(3) C(59)—C(58)—C(63) 119.3(3) C(58)—C(59)—C(54)119.3(3) C(58)—C(59)—C(64) 121.0(3) C(54)—C(59)—C(64) 119.8(2)O(3)—C(65)—C(70) 122.6(3) O(3)—C(65)—C(66) 122.2(3) C(70)—C(65)—C(66)115.2(3) F(11)—C(66)—C(67) 118.2(3) F(11)—C(66)—C(65) 119.4(2)C(67)—C(66)—C(65) 122.4(3) F(12)—C(67)—C(68) 120.0(3) F(12)—C(67)—C(66)119.9(3) C(68)—C(67)—C(66) 120.1(3) F(13)—C(68)—C(69) 120.8(3)F(13)—C(68)—C(67) 120.2(4) C(69)—C(68)—C(67) 119.0(3) F(14)—C(69)—C(68)120.8(3) F(14)—C(69)—C(70) 118.4(4) C(68)—C(69)—C(70) 120.8(3)F(15)—C(70)—C(69) 119.2(3) F(15)—C(70)—C(65) 118.4(3) C(69)—C(70)—C(65)122.4(3) O(4)—C(71)—C(76) 122.3(2) O(4)—C(71)—C(72) 122.3(3)C(76)—C(71)—C(72) 115.4(2) F(20)—C(72)—C(73) 118.9(3) F(20)—C(72)—C(71)119.5(3) C(73)—C(72)—C(71) 121.6(3) F(19)—C(73)—C(72) 120.0(3)F(19)—C(73)—C(74) 118.4(3) C(72)—C(73)—C(74) 121.5(3) F(18)—C(74)—C(73)121.8(3) F(18)—C(74)—C(75) 120.0(4) C(73)—C(74)—C(75) 118.2(3)F(17)—C(75)—C(76) 120.3(3) F(17)—C(75)—C(74) 119.9(3) C(76)—C(75)—C(74)119.7(3) F(16)—C(76)—C(75) 119.1(3) F(16)—C(76)—C(71) 117.4(3)C(75)—C(76)—C(71) 123.4(3)

TABLE 3 Anisotropic displacement parameters [A² × 10³]. The anisotropicdisplacement factor exponent takes the form: −2□²[(ha*)²U₁₁ + . . . +2hka * b * U₁₂]. U₁₁ U₂₂ U₃₃ U₂₃ U₁₃ U₁₂ Zr(1) 38(1) 32(1) 40(1) −1(1)12(1)  6(1) O(1) 56(1) 34(1) 60(1) 7(1) 28(1) 11(1) O(2) 39(1) 66(1)64(1) −3(1)  9(1)  4(1) N(1) 46(1) 37(1) 43(1) −2(1) 14(1)  6(1) N(2)62(2) 39(1) 47(1) 2(1) 10(1) 14(1) N(3) 50(1) 36(1) 46(1)  3(1) 19(1) 1(1) F(1) 48(1) 68(1) 90(1) −2(1)  7(1) 13(1) F(2) 94(2) 75(1) 133(2) −54(1)  −16(2)  17(1) F(3) 109(2)  68(1) 165(3)  −40(1)  −6(2) 49(1)F(4) 73(2) 85(2) 139(2)  −16(1)  −18(2)  40(1) F(5) 75(1) 62(1) 90(2)−22(1)  −7(1)  9(1) F(6) 65(1) 92(2) 120(2)  −46(1)  11(1) 14(1) F(7)62(1) 112(2)  128(2)  −31(2)  13(1) 35(1) F(8) 40(1) 103(2)  88(2) 25(1) 0(1)  3(1) F(9) 62(1) 62(1) 139(2)  20(1) −11(1)  −9(1) F(10) 56(1)55(1) 157(2)  17(1) −7(1)  9(1) C(1) 71(2) 39(1) 53(2) −7(1) 19(2) 12(1)C(2) 67(2) 39(1) 68(2) −3(1) 18(2) 17(1) C(3) 79(2) 33(1) 66(2)  7(1)26(2)  4(1) C(4) 81(2) 44(2) 62(2) 10(1) 31(2)  5(2) C(5) 51(2) 38(1)39(1) −8(1) 18(1)  4(1) C(6) 55(2) 48(2) 50(2) −12(1)  26(1) −1(1) C(7)70(2) 54(2) 54(2) −8(1) 35(2) −7(2) C(8) 85(3) 50(2) 45(2) −4(1) 30(2) 2(2) C(9) 63(2) 48(2) 43(2) −7(1) 15(1)  5(1) C(10) 50(2) 38(1) 41(1)−7(1) 15(1)  1(1) C(11) 53(2) 73(2) 78(2) −12(2)  31(2) −1(2) C(12)105(3)  99(3) 82(3)  0(2) 57(3) −21(2)  C(13) 116(4)  91(3) 51(2) 11(2)33(2)  5(2) C(14) 74(3) 91(3) 51(2)  6(2)  6(2) 13(2) C(15) 46(2) 65(2)55(2)  1(1) 16(2)  1(1) C(16) 41(2) 41(1) 36(1)  3(1) 15(1)  0(1) C(17)43(2) 53(2) 36(1) −4(1) 13(1) −3(1) C(18) 42(2) 61(2) 47(2)  4(1) 14(1) 8(1) C(19) 53(2) 46(2) 57(2) −3(1) 22(2)  2(1) C(20) 50(2) 46(2) 49(2)−10(1)  13(1) −7(1) C(21) 40(2) 46(1) 43(2)  2(1) 10(1) −4(1) C(22)50(2) 88(2) 51(2) −16(2)  11(2) −8(2) C(23) 51(2) 115(3)  71(2)  0(2)14(2) 25(2) C(24) 74(3) 67(2) 101(3)  −19(2)  35(2) 13(2) C(25) 75(3)83(3) 87(3) −44(2)  15(2) −11(2)  C(26) 49(2) 80(2) 51(2) −2(2)  3(2) 7(2) C(27) 49(2) 33(1) 52(2)  5(1) 20(1)  8(1) C(28) 43(2) 47(2) 65(2) 4(1) 13(2)  9(1) C(29) 59(2) 49(2) 79(2) −19(2)   6(2)  6(2) C(30)71(2) 44(2) 98(3) −14(2)   9(2) 24(2) C(31) 54(2) 52(2) 87(2) −2(2)−1(2) 19(2) C(32) 56(2) 41(2) 65(2) −5(1)  9(2)  7(1) C(33) 38(2) 68(2)47(2)  5(1)  9(1)  6(1) C(34) 54(2) 71(2) 65(2) −16(2)  18(2)  5(2)C(35) 44(2) 92(3) 73(2) −1(2) 15(2) 24(2) C(36) 39(2) 80(2) 63(2) 16(2) 8(2)  2(2) C(37) 46(2) 58(2) 72(2) 18(2)  5(2) −4(1) C(38) 44(2) 55(2)75(2) 21(2)  7(2)  3(1) Zr(2) 37(1) 35(1) 39(1)  5(1) 12(1)  5(1) O(3)63(1) 47(1) 61(1) −1(1) 20(1) 18(1) O(4) 55(1) 46(1) 63(1) 17(1) −5(1)−3(1) N(4) 41(1) 47(1) 46(1) 10(1) 17(1)  3(1) N(5) 50(2) 45(1) 55(2)13(1) 12(1)  5(1) N(6) 39(1) 48(1) 42(1)  9(1)  9(1)  2(1) N(7) 53(2)51(1) 46(1)  0(1) 12(1) −2(1) F(11) 94(2) 63(1) 70(1)  4(1) 36(1)  9(1)F(12) 69(1) 105(2)  85(2) −25(1)  28(1) 18(1) F(13) 80(2) 71(1) 124(2) −30(1)   8(1) 39(1) F(14) 102(2)  41(1) 127(2)   7(1) 17(2) 12(1) F(15)80(1) 54(1) 103(2)   8(1) 36(1)  4(1) F(16) 59(1) 62(1) 116(2)  −31(1)  1(1) 22(1) F(17) 78(2) 148(2)  80(2) −27(1)  41(1) −18(2)  F(18)122(2)  98(2) 82(2) 39(1) 16(2) −31(1)  F(19) 122(2)  43(1) 126(2) 15(1) 14(2) 33(1) F(20) 91(2) 81(1) 93(2)  4(1) 47(1) 28(1) C(39) 64(2)78(2) 55(2) 21(2) 26(2)  7(2) C(40) 65(2) 68(2) 46(2) 18(1) 16(2)  6(2)C(41) 50(2) 68(2) 60(2) 23(2)  4(2) 11(2) C(42) 46(2) 68(2) 59(2) 18(2) 2(2)  1(1) C(43) 44(2) 43(1) 49(2)  4(1) 21(1) −1(1) C(44) 45(2) 46(1)53(2)  1(1) 21(1)  5(1) C(45) 49(2) 71(2) 66(2)  0(2) 22(2) 14(2) C(46)42(2) 105(3)  61(2) −11(2)  14(2)  2(2) C(47) 52(2) 76(2) 67(2) −22(2) 25(2) −15(2)  C(48) 54(2) 44(2) 67(2) −8(1) 33(2) −6(1) C(49) 66(2)49(2) 76(2) −14(2)  34(2) −2(2) C(50) 75(3) 99(3) 114(3)   8(3) 24(3)45(2) C(51) 58(3) 199(6)  100(4)  −31(4)  −4(3) 19(3) C(52) 86(3)125(4)  113(4)  −61(3)  39(3) −46(3)  C(53) 92(3) 40(2) 95(3) −4(2)56(2) −6(2) C(54) 31(1) 43(1) 42(1) −2(1)  7(1) −2(1) C(55) 34(1) 50(2)43(1)  0(1)  9(1)  5(1) C(56) 34(1) 55(2) 43(2)  2(1)  9(1) −1(1) C(57)43(2) 46(2) 49(2) −2(1)  7(1) −7(1) C(58) 47(2) 43(1) 51(2) −12(1) 11(1) −5(1) C(59) 38(2) 52(2) 44(2) −8(1) 12(1) −4(1) C(60) 45(2) 60(2)69(2)  4(2) 21(2) 15(1) C(61) 61(2) 76(2) 78(2) 12(2) 34(2)  4(2) C(62)79(3) 49(2) 79(2)  4(2) 25(2) −12(2)  C(63) 87(3) 47(2) 97(3) −17(2) 39(2)  1(2) C(64) 64(2) 66(2) 62(2) −12(2)  31(2) −7(2) C(65) 45(2)42(1) 56(2) −4(1)  3(1) 13(1) C(66) 50(2) 53(2) 52(2) −9(1)  7(1) 11(1)C(67) 42(2) 73(2) 61(2) −18(2)   7(2) 11(2) C(68) 49(2) 55(2) 78(2)−21(2)  −2(2) 20(2) C(69) 60(2) 39(2) 80(2)  1(2) −3(2) 11(1) C(70)50(2) 49(2) 67(2) −2(1) 14(2)  6(1) C(71) 44(2) 34(1) 49(2)  5(1)  0(1) 3(1) C(72) 54(2) 46(2) 54(2)  1(1) 16(2) 13(1) C(73) 70(2) 36(1) 67(2) 5(1)  3(2) 11(1) C(74) 66(2) 60(2) 55(2) 12(2)  5(2) −14(2)  C(75)49(2) 82(2) 54(2) −11(2)  14(2) −10(2)  C(76) 42(2) 45(2) 61(2) −10(1)  2(1)  7(1) C(77) 58(2) 73(2) 53(2)  2(2) −2(2)  4(2) C(78) 81(3) 80(2)52(2) −17(2)  17(2)  3(2)

TABLE 4 Hydrogen atom coordinates (×10⁴) and isotropic displacementparameters (A² × 10³) x y z U(eq) H(2) 2630(20) 10559(19) 965(18) 60H(1A) 4196 11047 2863 65 H(1B) 3221 10868 3126 65 H(2A) 2166 10881 194870 H(2B) 2987 11645 1958 70 H(3A) 4622 10995 1738 70 H(3B) 3965 114891050 70 H(4A) 3914 10353 233 72 H(4B) 5054 10444 745 72 H(11A) 1687 85352905 99 H(11B) 1948 9511 2751 99 H(11C) 1585 9298 3453 99 H(12A) 21998688 4825 135 H(12B) 2622 7756 4847 135 H(12C) 1845 8050 4109 135 H(13A)4297 8426 5792 126 H(13B) 5229 8033 5613 126 H(13C) 4157 7520 5345 126H(14A) 6577 9130 4662 111 H(14B) 6286 8257 4996 111 H(14C) 6255 91635402 111 H(15A) 6105 10126 3909 83 H(15B) 5407 10013 3073 83 H(15C) 60859258 3434 83 H(22A) 6586 8861 2117 97 H(22B) 5892 9626 1809 97 H(22C)6875 9513 1567 97 H(23A) 7660 8287 1248 119 H(23B) 7453 7311 932 119H(23C) 7252 7570 1693 119 H(24A) 5530 6308 −478 118 H(24B) 6378 6332 300118 H(24C) 6549 6883 −355 118 H(25A) 4448 7014 −1242 128 H(25B) 34507416 −1191 128 H(25C) 3782 6542 −797 128 H(26A) 2638 7966 −372 94 H(26B)3030 8639 −859 94 H(26C) 2891 8952 −90 94 H(5) −150(20) 6080(20)1661(17) 60 H(7) 2140(20) 5640(20) 3781(17) 61 H(39A) 1722 5047 1137 76H(39B) 1556 5995 1412 76 H(40A) 41 5566 584 71 H(40B) 68 4610 879 71H(41A) −1656 5480 793 74 H(41B) −1691 5626 1625 74 H(42A) −2274 42181365 73 H(42B) −1510 4036 906 73 H(49A) 2864 3387 1649 92 H(49B) 18463711 1736 92 H(49C) 2476 3079 2317 92 H(50A) 4159 2975 2812 142 H(50B)5211 3456 3251 142 H(50C) 4822 3456 2371 142 H(51A) 5807 4442 4045 188H(51B) 5937 5468 4134 188 H(51C) 6155 4983 3451 188 H(52A) 4316 70873675 164 H(52B) 5358 6695 3725 164 H(52C) 4807 6479 4330 164 H(53A) 27266889 3422 105 H(53B) 1906 6554 2670 105 H(53C) 2897 7093 2647 105 H(60A)−1981 4504 2684 85 H(60B) −2234 4046 3356 85 H(60C) −3039 3989 2557 85H(61A) −2592 2595 3815 103 H(61B) −3147 1747 3345 103 H(61C) −3488 26743076 103 H(62A) −2695 581 2804 104 H(62B) −1891 872 3576 104 H(62C)−1563 346 2962 104 H(63A) −102 717 2503 113 H(63B) −466 924 1649 113H(63C) −1186 363 1998 113 H(64A) −164 3064 1326 93 H(64B) −434 2063 110693 H(64C) 499 2363 1802 93 H(77A) 3080 4872 4588 98 H(77B) 2681 42723850 98 H(77C) 2188 4155 4502 98 H(78A) 951 5239 4640 108 H(78B) 10906154 4310 108 H(78C) 1999 5790 4924 108

Example 4 (Comparative Example # 1): HN5Zr(NMe₂)₂

100 ml of hexane was added to 3.00 g (11.21 mmol) of (2) HN5(HN(CH₂CH₂NHC₆(CH₃)₅)₂) and allowed to stir for ten minutes.Tetrakis(dimethylamino)zirconium (4.43 g, 11.21 mmol) was added to theslurry and left to stir for 19 hours. The heterogeneous solution wasconcentrated to half volume. The resulting tan precipitate was isolatedby filtration and the remaining volatiles were removed by vacuum. Totalyield of desired product was 5.14 g (80%). The kinetic parameters arelisted in Table 5 below. ¹H NMR (C₆D₆): δ 1.85 (br m, 1H), 2.14 (s, 6H),2.20 (s, 6H), 2.22 (s, 6H), 2.24 (s, 6H), 2.50 (s, 6H), 2.53 (s, 6H),2.68 (m, 4H), 3.04 (m, 2H), 3.12 (s, 6H), 3.37 (m, 2H).

Example 5 (Comparative Example #2): HN5ZrCl₂

100 ml ether was added to a flask charged with 2.0 g (4.348 mmol) of (5)HN5Zr(NMe₂)₂. Next, 1.2 mL of chlorotrimethylsilane (9.1302 mmol) wasadded to the ether solution and allowed to stir for 19 hours. Volatileswere removed by vacuum and a tan powder remained. The powder was washedwith hexane and filtered through a medium fritted filter.Recrystallization from toluene produced 1.53 g (63%) of the desiredproduct. The kinetic parameters are listed in Table 5 below. ¹H NMR(C₆D₆): δ 2.05 (s, 6H), 2.07 (s, 6H), 2.14 (s, 6H), 2.47 (s, 6H), 2.50(s, 6H), 2.57 (m, 5H), 2.94 (m, 2H), 3.40 (m, 2H).

TABLE 5 Kinetic Parameters of Examples 1-5 Productivity kp (gPE/mmol(gPE/mmol ki t_(1/2) Zr/hr/100 psi) Zr/hr/100 psi) (min−1) (min) EX. 1:HN5Zr(OC₆F₅)₂ 1.2(1) × 10⁴ 2.3(1) × 10⁴ 3.0(9) × 10⁻¹   9(1) × 10¹ EX.2: HN5Zr(OC₆F₅)₂ 1.2(1) × 10⁴ 2.3(1) × 10⁴ 3.0(9) × 10⁻¹   9(1) × 10¹EX. 3: HN5Zr(NMe₂)(OC₆F₅)   9(2) × 10³ 2.0(4) × 10⁴ 2.0(6) × 10⁻¹   6(1)× 10¹ EX. 4: HN5Zr(NMe₂)₂ 2.5(6) × 10³ 2.0(2) × 10⁴   7(1) × 10⁻¹ 1.0(1)× 10¹ EX. 5: HN5ZrCl₂ 1.2(1) × 10⁴ 2.9(9) × 10⁴   3(2) × 10⁻¹   7(2) ×10¹

General Procedure for Polymerization:

A computer controlled, one liter 316 stainless steel reactor withair-operated two-wing paddle and an inner steam-heated shell and anouter water-cooled shell was dried by heating to 135° C. while purgingwith 500 sccm of nitrogen for 30 minutes. After cooling to 50° C., itwas charged with 600 mL hexane and 43 mL 1-hexene under inertconditions. A catalyst charging vessel comprising a ¼ inch (0.64 cm)×2″(5 cm) stainless steel tube isolated between two ball valves with a 25mL stainless steel reservoir on top was charged with the polymerizationcatalyst in a drybox. A vessel atop this was charged with 5 mL dryhexane. The entire assembly was then attached to the reactor against anitrogen purge. The reservoir containing hexane above the injection tubewas pressurized to 250 psi with nitrogen. A solution of 100 micromolesof tri-isobutylaluminum (TIBA) and 2 mL 1-hexene was then added to thereactor and the reactor sealed. When the reactor reached conditions (130psi ethylene, 85° C., 40 minutes), the catalyst was injected using thenitrogen pressure from the reservoir and held at conditions for therequisite time. The reaction was ended by venting and cooling.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties, reaction conditions, and so forth, used in thespecification and claims are to be understood as approximations based onthe desired properties sought to be obtained by the present invention,and the error of measurement, etc., and should at least be construed inlight of the number of reported significant digits and by applyingordinary rounding techniques. Notwithstanding that the numerical rangesand values setting forth the broad scope of the invention areapproximations, the numerical values set forth are reported as preciselyas possible.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted. Further, alldocuments cited herein, including testing procedures, are herein fullyincorporated by reference for all jurisdictions in which suchincorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A catalyst system comprising a catalyst represented by the formula:α_(a)β_(b)γ_(g)MX_(n) wherein M is a metal; X is a halogenated aryloxygroup; β and γ are groups that each comprise at least one Group 15 atom;α is a linking moiety that forms a chemical bond to each of β and γ; a,b, g, and n are each integers from 1 to
 4. 2. The catalyst system ofclaim 1, wherein the halogenated aryloxy group comprises aperfluorophenoxy group.
 3. The catalyst system of claim 1, wherein thecatalyst system is supported on a carrier.
 4. The catalyst system ofclaim 1, wherein the catalyst system further comprises an activator. 5.The catalyst system of claim 1, wherein M is selected from the groupconsisting of titanium, zirconium, and hafnium.
 6. The catalyst systemof claim 1, further comprising one or more metallocene catalystsrepresented by the formula:Cp^(A)Cp^(B)MX_(n) wherein: M is a metal atom; Cp^(A) and Cp^(B) areeach independently an unsubstituted or substituted cyclic ring group; Xis a leaving group; and n is zero or an integer from 1 to
 4. 7. Thecatalyst system of claim 6, wherein Cp^(A) and Cp^(B) are eachindependently selected from the group consisting of cyclopentadienyl,indenyl, combinations thereof, and derivatives thereof.
 8. The catalystsystem of claim 6, wherein Cp^(A) is a cyclopentadienyl group and Cp^(B)is an indenyl group.
 9. The catalyst system of claim 6, wherein Cp^(A)is a cyclopentadienyl group and Cp^(B) is an indenyl group and the oneor more polymerization catalysts comprises a bridging group A, bridgingCp^(A) and Cp^(B).
 10. The catalyst system of claim 6, wherein Cp^(A) isa cyclopentadienyl group and Cp^(B) is a cyclopentadienyl group.